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Physics KimFundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 1
1. Consider a two-dimensional lattice shown in Figure 1, left. One half of the molecules in this
lattice have been modified in a regular way so that their atoms now have sad faces, as shown
in Figure 1, right. This may be a schematic illustrating the formation of a magnetically
ordered structure, where happy and sad faces represent opposite directions of magnetic
moments. Suggest the most probable unit cell in this new lattice assuming that the correct
unit cell in the original lattice is shown by a yellow shaded parallelogram.
Figure 1. The original lattice containing indistinguishable molecules in which a proper unit cell is
shaded yellow (left) and a new lattice derived by switching ½ of atoms from happy (green) to sad (red)
faces in a regular fashion.
Solution
We know (sections 1.2 and 1.3) that in a lattice, all elementary parallelepipeds (unit cells) are
equal in their shape and content, so if the distribution of atoms in one unit cell is known, the
whole crystal can be constructed by simply propagating (translating or shifting) this unit cell
along one, two or three directions independently. Based on this definition, a possible solution
of the problem is shown in Figure 2, right. The appearance of distinguishable molecules
requires doubling the volume (area in two dimensions) of the unit cell, i.e. it should contain
two molecules.
Figure 2. The original lattice containing indistinguishable molecules in which a proper unit cell is
shaded (left) and a new lattice derived by switching ½ of atoms from happy to sad faces in a regular
fashion. The most probable unit cell based on the diagonals of the original unit cell is shaded in light
green.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Consider a two dimensional non-orthogonal lattice shown in Figure 3. Sketch the following
sets of crystallographic planes: (12), (2), (3).
Figure 3. The two dimensional non-orthogonal lattice with the unit cell shown in bold.
Solution
The (12) planes are shown in Figure 4, the (2) in Figure 5, and the (3) planes in Figure 6.
(12)
Figure 4. The set of crystallographic planes (12) shown as red lines.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
(2)
Figure 5. The set of crystallographic planes (2) shown as red lines.
(3)
Figure 6. The set of crystallographic planes (3) shown as red lines.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. A monoclinic lattice has the following unit cell dimensions: a = 5.00 Å, b = 10.0 Å, c =
8.00 Å, and β = 110º. Calculate the unit cell dimensions of the corresponding reciprocal
lattice.
Solution
The volume of the monoclinic unit cell is the area of the parallelogram ac multiplied by
b: V = acsin(β)b = 5·8·sin(110º)·10 = 375.9 Å3. The relevant cross products are: |bc| =
10·8·sin(90º) = 80 Å2, |ac| = 5·8·sin(110º) = 37.59 Å2, and |ab| = 5·10·sin(90º) = 50 Å2.
Hence, a* = |bc|/V = 0.213 Å-1, b* = |ac|/V = 0.100 Å-1, and c* = |ab|/V = 0.133 Å-1.
Considering Figure 7, the angle β* is equal to 180º - β. Hence, β* = 70º.
(001) (001) (001)
a
(100)
(100)
(100)
(100)
90º
c
c* 90º
*=180º-
a*
Figure 7. The schematic of the ac plane of the direct monoclinic lattice with the (100) and (001) planes
shown (thin lines) and vectors a* and c* of the corresponding reciprocal lattice shown in bold. Vectors a*
and c* are perpendicular to the (100) and (001) planes, respectively.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 2
1. Consider two mirror planes that intersect at = 90°. Using geometrical representation of two
planes establish which symmetry element(s) appear as the result of this combination of mirror
planes. What is(are) the location(s) of new symmetry element(s)? Name point group
symmetry formed by this combination of symmetry elements.
Solution
The solution is given in Figure 8. Point group symmetry is mm2.
Figure 8. Mirror planes intersecting at = 90o produce a total of four symmetrically equivalent
objects starting from any object (left). The resulting new symmetry element is a two-fold axis
(right), coinciding with the line along which the planes intersect. Symmetrical relationships are
shown using dash-dotted arrows.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Consider two mirror planes that intersect at = 45°. Using geometrical representation of two
planes establish which symmetry element(s) appear as the result of this combination of mirror
planes. What is(are) the location(s) of new symmetry element(s)? Name point group
symmetry formed by this combination of symmetry elements.
Solution
The solution is given in Figure 9. Point group symmetry is 4mm.
Figure 9. Two mirror planes intersecting at = 45o produce a total of eight symmetrically equivalent
objects starting from any object (left). The resulting new symmetry elements (right) are: a four-fold
axis, coinciding with the line along which the planes intersect and two mirror planes. All planes
intersect along the same line and form a 45o angle between any pair of neighboring planes.
Symmetrical relationships are shown using dash-dotted arrows.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. Consider the following sequence of numbers: 1, ½, ⅓, ¼, …, 1⁄N, ... Is this a group assuming
that the combination law is multiplication, division, addition or subtraction? If yes, identify
the combination law in this group and establish whether this group is finite or infinite.
Solution
Consider multiplication as the combination law. To find out whether the infinite sequence of
simple fractions, 1/N, where N = 1, 2, 3, …, forms a group we need to verify that all four
properties of a group hold.
1 1 1 1
Is the group closed? , where N3 = N1N2. Yes, the group is
N1 N 2 ( N1 N 2 ) N 3
closed since a combination (multiplication) of any two elements that belong to the group
is also an element of the group.
Does the associative law holds?
1 1 1 1 1 1 1
( ) ( ) . Yes, the associative law holds
N1 N 2 N 3 N1 N 2 N 3 ( N1 N 2 N 3 )
since the resultant fraction is independent of the order in which multiplication has been
carried out.
1 1 1 1
Is there one and only one unity element? . Yes, unity element is
1 N 1 (1 N 1 ) N 1
1 (or 1/1).
Is there one and only one inverse element for every element of the group?
1 N1 1
1 . An inverse of a fraction 1/N when the combination law is
N1 1 1
multiplication is an integer, N. There are no integers, except 1, in this infinite series of
simple fractions. Therefore, this is not a group when the combination law is
multiplication.
Examination of division, addition and subtraction as the combination laws leads to the
1 1 N 1
conclusion that the group is not closed because in general / 2 and
N1 N 2 N1 N 3
1 1 N N1 1
2 . Therefore, we conclude that the sequence of numbers: 1,
N1 N 2 N1 N 2 N 3
½, ⅓, ¼, …, 1/N, ... is not a group for any of the four binary combinations laws considered
above.
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4. Consider the group created by three non-coplanar translations (vectors) using the combination
law defined by Eq. 1.1 in section 1.3. Which geometrical form can be chosen to illustrate this
group? Is the group finite?
Solution
As shown in Figure 10, a lattice built on these three non-coplanar vectors is a geometrical
representation of the group. The group is infinite.
Figure 10. Three non-coplanar vectors a, b and c (left) create a crystallographic lattice (right) where
each point is defined by a vector q = ua + vb + wc and u, v and w are integers. Two vectors with u = -2,
v = -1, w = 2; and u = 3, v = 2, w = 2 are shown in blue and red, respectively.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. Determine both the crystal system and point group symmetry of a parallelepiped (a brick),
which is shown schematically in Figure 11 and in which a b c and = = = 90°?
c
a
b
Figure 11. Illustration of a parallelepiped (a brick) in which three independent edges have different
lengths.
Solution
As shown in Figure 12, the point group symmetry of a brick is mmm and it belongs to the
orthorhombic crystal system.
Figure 12. Symmetry elements present in a brick: three mutually perpendicular mirror planes
(white), three two-fold axes coinciding with the lines at which pairs of planes intersect (grey), and
a center of inversion in a point of intersection of all planes and all axes (light blue).
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
6. Determine both the crystal system and point group symmetry of benzene molecule, C6H6,
which is shown in Figure 13. Treat atoms as spheres, not as dimensionless points.
Figure 13. The schematic of benzene molecule. Carbon atoms are red and hydrogen atoms are blue.
Solution
As shown in Figure 14, the point group symmetry of benzene molecule is 6/mmm and it
belongs to the hexagonal crystal system.
Figure 14. Symmetry elements present in benzene molecule (carbon atoms are red, hydrogen atoms are
blue): 6 mirror planes, perpendicular to the plane of the projection, 30o apart; one mirror plane in the
plane of the projection; six-fold axis, coinciding with the line at which six plane intersect, 6 two-fold
axes in the plane of the projection and a center of inversion in the point where all planes and axes
intersect.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
7. Determine both the crystal system and point group symmetry of the ethylene molecule, C2H4,
shown schematically in the figure below. Using the projection on the left, show all symmetry
elements that you were able to identify in this molecule, include both the in-plane and out-of-
plane symmetry elements. Note: treat atoms as spheres, not as dimensionless points.
y z
x x
Figure 15. The schematic of ethylene molecule. Carbon atoms are red and hydrogen atoms are blue.
Solution
As illustrated in Figure 16, there are 7 symmetry elements in the ethylene molecule: 3
mutually perpendicular mirror planes, three mutually perpendicular two-fold axes, and a
center of inversion. The crystal system is orthorhombic and point groups symmetry is mmm.
y
Figure 16. The schematic of ethylene molecule with all symmetry elements shown.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
8. Determine the point group symmetry of the octahedron. How many and which symmetry
elements are present in this point group symmetry?
Solution
As shown in Figure 17, the point group symmetry of the octahedron is mm. It contains
the following symmetry elements: 3 four-fold rotation axes; 4 three-fold rotoinversion
axes; 6 two-fold rotation axes; 9 mirror planes; 1 center of inversion.
Figure 17. The schematic of an octahedron (left) and the stereographic projection of all symmetry
elements present in the octahedron (right).
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
9. The following relationships between lattice parameters: a b c, 90 or 120º, and =
90º potentially define a "diclinic" crystal system (two angles 90º). Is this an eighth crystal
system? Explain your answer.
Solution
This is a triclinic crystal system, since the symmetry of the unit cell shape is .
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10. The relationships a = b c, = = 90º, and 90º point to a monoclinic crystal system,
except that a = b. What is the reduced (standard) Bravais lattice in this case? Provide
equations that reduce this lattice to one of the 14 standard Bravais types.
Solution
This is the base centered orthorhombic lattice with the reduced unit cell: a'=a+b, b'=a-b,
c'=c) as shown in Figure 18.
Figure 18. The projection of the original monoclinic lattice with a = b c and = = 90o and 90o
along the c axis (black) and the reduced orthorhombic base-centered unit cell (red).
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
11. Imagine that there is an "edge-centered" lattice (for example unit cell edges along Z contain
lattice points at ½c). If this were true, the following lattice translation is present: (0, 0, ½).
Convert this lattice to one of the standard lattices.
Solution
The translation 0, 0, ½ indicates that every atom with the coordinates x, y, z has
symmetrically equivalent atom at x, y, z + ½ Hence, the “lower” half of the unit cell is the
same as the “upper” half of the unit cell along Z axis. The unit cell is doubled and can be
transformed to a standard setting by selecting a smaller unit cell with c’ = c/2. After this
transformation the earlier "edge centering” translation (0, 0, ½) becomes (0, 0, 1), which is
one of the standard lattice translations.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
12. Monoclinic crystal system has primitive and base-centered Bravais lattices (see Table 2.13).
Using two-dimensional projections from Figure 19 show how a body-centered lattice and a
face-centered monoclinic lattice (their unit cells are indicated with the dashed lines) can be
reduced to a base-centered lattice. Write the corresponding vectorial relationships between
the unit cell vectors of the original body-centered and face-centered lattices and the
transformed base-centered lattices. What are the relationships between the unit cell volumes
of the original body- and face-centered lattices and the resulting base-centered lattices?
z I z F
x x
Notes: y is perpendicular to the paper
- point at y = 0, 1, …
- point at y = ½, 3/2, …
Figure 19. Body centered (left) and face centered (right) monoclinic lattices projected along the Y-axis
with the corresponding unit cells shown using the dashed lines.
Solution
The solution is depicted in Figure 20. The corresponding transformations of vectors are as
follows.
aC = aI + cI, cC = -cI, and bC = bI
aC = -cF, cC = ½(aF + cF), and bC = bF
The unit cell volumes are identical for the body-centered and the transformed base-centered
lattices since the area of a parallelogram is its base times height. The volume of the
transformed base-centered unit cell is half the volume of the original face-centered cell.
z C x C
x z
Figure 20. Correct face centered unit cells are sown using bold red lines.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 3
1. Consider space group symmetry Fdd2. Without using the International Tables for
Crystallography establish the following: (a) the crystal system; (b) the corresponding point
group symmetry; (c) the corresponding Laue class; (d) the relationships between the unit cell
dimensions; and (e) explain the space group symbol.
Solution
(a) – The crystal system is orthorhombic;
(b) – The point group symmetry is mm2;
(c) – The Laue class is mmm;
(d) – The relationships between the unit cell dimensions are as follows: a b c, and = =
= 90o;
(e) – The space group symbol indicates the following: Bravais lattice is face-centered,
diamond glide planes, d, perpendicular to X and Y, and two-fold axis parallel to Z).
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Consider orthorhombic space group symmetry Pnma
On what point group symmetry this space group is based upon?
When X and Y directions are switched, one obtains a different setting of the same space group
– Pmnb. In as few sentences as possible, yet fully, explain why not Pmna. If you think
a sketch helps, supplement your explanations with a figure.
Considering all possible permutations of X, Y and Z axes, find all valid non-standard settings
of this space group.
Solution
2.1 mmm
2.2 When X and Y are switched, Z remains the same. In the standard setting the glide plane
a translates along X (i.e. the direction to which plane n is perpendicular). In the new
setting, this direction is Y, and therefore, glide plane a in the third position is converted
to the glide plane b (in this setting, this glide plane translates along the Y direction).
2.3 xyz: Pnma
yxz: Pmnb
xzy: Pnam
yzx: Pmcn
zxy: Pbnm
zyx: Pcmn
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. Consider orthorhombic space group symmetry P2mb, see Figure 21. Similar to as this is
done in the International Tables for Crystallography, list multiplicities and coordinates of all
symmetrically equivalent points for each independent site position (general and special, if
any) in this space group symmetry and briefly explain your answers.
Y x,0,0
Figure 21. Combination of symmetry elements in one unit cell (thin lines) for space group symmetry
P2mb. The origin of coordinates is on the two-fold axis marked by arrow.
Solution
As shown in Figure 22 – Figure 25, there is one general site (an atom is not located on any of
the finite symmetry elements) and three special sites in this space group symmetry. The
following are the coordinates of the symmetrically equivalent atoms for each of the sites and
the corresponding Wyckoff notations (note, that the x coordinate remains unchanged because
the only symmetry element perpendicular to the X-axis and the plane of the projection is 1):
4(d) x,y,z; x,½-y,z; x, ½ +y,-z; x,-y,-z (Figure 22)
2(c) x,¼,z; x,¾,-z (Figure 23)
2(b) x,0,½; x,½,½ (Figure 24)
2(a) x,0,0; x,½,0 (Figure 25)
Remember that the difference by a full translation in one, two or three directions refers to the
same position.
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Y x,0,0
z z
Z
y ½-y
½+y -y
-z -z
Figure 22. Symmetrically equivalent atoms and their coordinates for the general site position in space
group symmetry P2mb.
Y x,0,0
z
Z
-z
Figure 23. Symmetrically equivalent atoms and their coordinates for the special site position on a
mirror plane in space group symmetry P2mb.
Y x,0,0
Z
x,0,½ x,½,½
Figure 24. Symmetrically equivalent atoms and their coordinates for the special site position on a two-
fold axis located at x,0,½ in space group symmetry P2mb.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Y x,0,0 x,½,0
Figure 25. Symmetrically equivalent atoms and their coordinates for the special site position on a two-
fold axis located at x,0,0 in space group symmetry P2mb.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
4. Consider independent atoms with the following coordinates in the space group symmetry
C2/m: Atom1: x = 0.15, y = 0.0, z = 0.33; Atom2: x = 0.5, y = 0.11, z = 0.5; and Atom3: x =
0.25, y = 0.25, z = 0.25. Using the International Tables for Crystallography carry out the
following tasks:
Apply the coordinates and centering vectors listed for the general equivalent position to
generate all symmetrically equivalent atoms from the three listed independent atoms (the total in
each case should be the same as the multiplicity of the general position).
Find atoms with equal coordinate triplets (remember that the difference by a full translation
in one, two or three directions refers to the same atom) and cross them out. The total number of
atoms left is the multiplicity of the corresponding special position.
Establish both the multiplicity and the Wyckoff notation of special position for each of the
three listed independent atoms.
To which symmetry element(s), if any, do the independent atoms belong?
Which of the three original independent atoms occupies the general equivalent position?
Solution
4.1 The general site position has the following coordinates:
1): x, y, z; 2): x, -y, z; 3): -x, y, -z; 4): -x, -y, -z;
plus a base centered translation: ½, ½, 0 – points 5), 6), 7), and 8).
Atom1: (x = 0.15, y = 0, z = 0.33)
1) 2) 3) 4)
0.15, 0, 0.33; 0.15, 0, 0.33; -0.15, 0, -0.33; -0.15, 0, -0.33;
5) 6) 7) 8)
0.65, 0.5, 0.33; 0.65, 0.5, 0.33; 0.35, 0.5, -0.33; 0.35, 0.5, -0.33;
Atom2: (x = 0.5, y = 0.11, z = 0.5)
1) 2) 3) 4)
0.5, 0.11, 0.5; 0.5, -0.11, 0.5; -0.5, 0.11, -0.5; -0.5, -0.11, -0.5;
5) 6) 7) 8)
1.0, 0.61, 0.5; 1.0, 0.39, 0.5; 0.0, 0.61, -0.5; 0.0, 0.39, -0.5;
Atom3: (x = 0.25, y = 0.25, z = 0.25)
1) 2) 3) 4)
0.25, 0.25, 0.25; 0.25, -0.25, 0.25; -0.25, 0.25, -0.25; -0.25, -0.25, -0.25;
5) 6) 7) 8)
0.75, 0.75, 0.25; 0.75, 0.25, 0.25; 0.25, 0.75, -0.25; 0.25, 0.25, -0.25;
4.2 The following coordinate triplets are identical for Atom1:
1) = 2); 3) = 4); 5) = 6); 7) = 8)
The multiplicity of the site is 4
The following coordinate triplets are identical for Atom2:
1) = 3); 2) = 4); 5) = 7); 6) = 8)
The multiplicity of the site is 4
There are no identical coordinate triplets for Atom3.
The multiplicity of the site is 8
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4.3 Atom1 belongs to a site 4(i): x, 0, z
Atom2 belongs to a site 4(h): 0, y, ½
Atom3 belongs to a site 8(j): x, y, z
4.4 Atom1 – m; Atom2 – 2; Atom3 – 1 (none)
4.5 Atom3
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. The crystal structure of a material is described in space group symmetry P63/mmc with the
following atomic coordinates:
Atom x y z
Ba1 0 0 0.25
Ba2 0.3333 0.6667 0.9110
Ni 0 0 0
Sb 0.3333 0.6667 0.1510
O1 0.4816 -0.0368 0.25
O2 0.1685 0.3370 0.4169
Using the International Tables for Crystallography describe every atom in terms of the
multiplicities and Wyckoff letters of their site positions and establish the content of the unit
cell, the simplest chemical formula and the number of formula units1 (Z) per unit cell.
Solution
The multiplicity and Wyckoff symbols are: Ba1 – 2(b), Ba2 – 4(f), Ni – 2(a), Sb – 4(f), O1 –
6(h), and O2 – 12(k). Note that atom O1 is in 6(h) position x,2x,1/4 but is listed in the table
with y=2x-1.The content of the unit cell is Ba6Ni2Sb4O18. The simplest chemical formula is
Ba3NiSb2O9. Number of formula units in the unit cell Z = 2.
1
Usually, a formula unit corresponds to the simplest chemical formula or to the stoichiometry of the
molecule of a material.
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6. Using a sheet of rectilinear graphing paper, draw a projection along the c-axis of one unit cell
of the crystal structure of an RX2 material that has the AlB2-type crystal structure. The space
group symmetry is P6/mmm. Assume that a = c = 4 Å. Atoms are located in the unit cell as
follows: R in 1(a) and X in 2(d), and both sites are fully occupied. Radius of atom R is larger
than that of atom X by ~30%. Prepare the drawing by hands and make sure that it is to scale,
including relative sizes of atoms (radii of circles). Mark elevations of all atoms above the
plane of the projections as their fractional coordinates along c accurate to 1/100.
Solution
The solution is show in Figure 26
R 0,1.00 0,1.00
a
X 0.50
0.50
0,1.00 0,1.00
Figure 26. The projection of one unit cell of an RX2 compound which crystallizes in the AlB2 type
structure.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 4
1. Two primitive orthorhombic space groups symmetry are based on the following symmetry
operations:
1 0 0 0 1 0 0 0 1 0 0 1/ 2
0 1 0 0 0 1 0 0 0 1 0 0
a)
0 0 1 0 0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1 0 0 0 1
1 0 0 0 1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0 0 1 0 0
b)
0 0 1 1/ 2 0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1 0 0 0 1
1.1 Identify these symmetry operations and write the international symbols of the two
space groups.
1.2 How can you describe the difference (if any) and/or similarity (if any) between these
two space groups?
Solution
1.1 a) Mirror plane m X; mirror plane m Y; glide plane a Z; space group Pmma
b) Glide plane c X; mirror plane m Y; mirror plane m Z; space group Pcmm
1.2 The two groups are identical. When X and Z directions are switched, Pmma is
converted into Pcmm and vise versa.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Two primitive orthorhombic space groups symmetry are based on the following symmetry
operations:
1 0 0 0 1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 1/ 2 0 1 0 0
a)
0 0 1 0 0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1 0 0 0 1
1 0 0 1/ 2 1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0 0 1 0 0
b)
0 0 1 0 0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1 0 0 0 1
2.1 Identify these symmetry operations and write the international symbols of the two
space groups.
2.2 How can you describe the difference (if any) and/or similarity (if any) between these
two space groups?
Solution
2.1 a) 2|| X 21||Y 2||Z; space group P2212
b) 21|| X 2||Y 2||Z; space group P2122
2.2 The two space group symmetries are identical (the similarity) except for the choice of
the coordinate system (the difference). Thus, space group symmetry P2212 is
converted into space group symmetry P2122 by switching X- and Y-axes. Both space
groups symmetry are non-standard settings of space group symmetry P2221, No. 17
according to the International Tables for Crystallography.
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3. Solve problem No. 2 in section 2.13. Find or derive symmetry operations (rotation matrices)
for both planes assuming that X-axis is left to right across the paper, Y-axis is bottom to top
along the paper, Z-axis is perpendicular to the paper, and the origin of coordinates is located
on the line along which the two planes intersect. Confirm the solution of problem No. 2 in
section 2.13 algebraically by finding all derivative symmetry operations. Relate symmetry
operations to the corresponding symmetry elements.
Solution
The solution of problem 2 in section 2.13 is shown in Figure 27.
45°
Figure 27. Starting from two mirror planes intersecting at 45º and a single point (left), we find that two
additional planes and a four-fold axis appear as the result (right). Dashed arrows show how
symmetrically equivalent points have been obtained. On the right, the original symmetry elements are
shown in black and the derivative symmetry elements are shown in blue.
Existing symmetry operations:
1 0 0
Unity: 0 1 0 (symmetry operation #1)
0 0 1
1 0 0
mX: 0 1 0 (symmetry operation #2)
0 0 1
0 1 0
m@45º to X: 1 0 0 (symmetry operation #3)
0 0 1
Algebraically, derivative symmetry operations are found by computing products of the
existing matrices. When a new matrix (symmetry operation) results, it is included in the
computations as shown below:
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11 = 1; 12 = 2; 13 = 3;
1 0 0 0 1 0 0 1 0
22 = 1; 23 = 0 1 0 1 0 0 1 0 0 , which is a new symmetry
0 0 1 0 0 1 0 0 1
operation, #4
In order not to miss any of the combinations it is best to create a table as shown below. Only
half of the table needs to be filled because the result is independent of the order in which
symmetry operations are applied (see section 2.5). New matrices are highlighted in yellow
and then moved to the top row and the leftmost column as shown by arrows to be included in
the computations. The order in which the table below has been filled is left to right, then top
to bottom
1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
Symmetry `
0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
operation 0 0 1 0
0 0 1
0 0 1
0 0 1
0 0 1
0 1 0
0 1 0 0 1
1 0 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
0 1 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
0 1 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
1 0 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
0 1 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
1 0 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
1 0 0 1 0 0 1 0 0 0 1 0 0 1 0
0 1 0 0 1 0 0 1 0 1 0 0 1 0 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
1 0 0 1 0 0 0 1 0 0 1 0
0 1 0 0 1 0 1 0 0 1 0 0
0 0 0 1
0 1 0 0 1
0 0 1
0 1 0 1 0 0 1 0 0
1 0 0 0 1 0 0 1 0
0 0 1 0 0 1 0 0 1
0 1 0 1 0 0
1 0 0 0 1 0
0 0 1 0 0 1
Copyright © 2009 by Springer 29
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
The correspondence of symmetry operations to symmetry elements illustrated in Figure 27 is
shown below.
1 mX m@45º X 4||Z mY 4||Z m@135º X 4||Z
1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0
0 1 0 0 1 0 1 0 0 1 0 0 0 1 0 0 1 0 1 0 0 1 0 0
0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1
Copyright © 2009 by Springer 30
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 5
1. When working with a modulated structure, researcher finds that the value of the modulation
vector q is (0, 0.172(1), 0). Is this one- two- or three-dimensional modulation? Is the
modulation commensurate or incommensurate?
Solution
This is a one-dimensional modulation because there is only one modulation vector.
Commensurability of the modulated structure can be established by considering whether or
not the periodicity of the modulation is commensurate with the periodicity of the lattice. The
period of the modulation function is = 1/q = 1/0.172 = 5.813953… Considering the error of
q, the period of the modulation function is 5.78035… < < 5.8479… Within a reasonable
accuracy, these values represent irrational numbers, and therefore, modulation in this
example is incommensurate (in other words the structure cannot be represented by a periodic
lattice with a reasonable unit cell.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. In another experiment, the modulation vector q is found to be (0.333(1), 0, 0.501(2)). How
many dimensions researcher needs to fully describe symmetry of this structure? She wonders
whether it will be possible to treat this crystal structure in three dimensions. Please, help her
in making the decision.
Solution
In order to fully describe conventional symmetry of a material one needs a set of
conventional 33 matrices and 31 vectors (or 44 augmented matrices). The fourth
dimension is added by a single modulation vector. Hence, one needs four dimensions to fully
describe symmetry of this material.
Within the error limits, the periodicity of the modulation function along X is = 1/0.333 3,
and it is = 1/0.501 2. Hence, the modulation is commensurate, and one needs to triple the
size of the unit cell along a, and double the unit cell along c in order to describe the crystal
structure of this material using conventional, three-dimensional symmetry.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. A quasicrystal has been described using a one-dimensional modulation function based on the
Fibonacci series. Starting from the origin, how many long and short structural fragments will
fit within the “period” No. 8.
Solution
Considering Table 5.1, when n = 7, the “LS” sequence is as follows:
LSLLSLSLLSLLSLSLLSLSLLSLLSLSLLSLLS (L = LS, S = L)
For n = 8, it becomes
LSLLSLSLLSLLSLSLLSLSLLSLLSLSLLSLLSLSLLSLSLLSLLSLSLLSLSL
Hence, “period” No. 8 should have 34 long fragments (L) and 21 short (S) fragments
Copyright © 2009 by Springer 33
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 6
1. A typical energy of electrons in a modern transition electron microscope is 300 keV.
Calculate the corresponding wavelength of the electron beam assuming that the vacuum inside
the microscope is ideal.
Solution
Electrons are charged particles with a non-zero rest mass. Considering Eq. 6.2, and recalling
that 1 eV = 1.60210-19 J = 1.60210-19 kgm2s-2 and that the mass of an electron is
9.10910-31 kg, velocity of the electron accelerated to 300 keV is
2 300,000eV 600,000 1.602 10 -19 kg m 2 s 2
v 1.0552 1017 3.248 108 m s 1
m 9.109 10 31 kg
From the de Broglie equation (Eq. 6.1), the wavelength of the 300 keV beam of electrons is
h 6.626 10-34 kg m 2 s -1
1
0.2240 10 11 m 0.0224 Å.
mv 9.109 10 kg 3.248 10 m s
-31 8
Copyright © 2009 by Springer 34
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Calculate the energy (in keV) of the characteristic Cr Kα1 and Mo Kα1 radiation.
Solution
hc hc
From Eq. 6.3 ( h ), the energy of a photon is E
Hence, for Cr Kα1 radiation
hc 6.626 10 34 J s 2.998 108 m s 1
E 8.676 10 16 J
2.28975 10 m -10
Recall that 1 eV = 1.60210-19 J. Hence, the energy of Cr Kα1 radiation is
8.676 10 16 J
E 5.415 keV
1.602 10-19 J (eV) -1
By repeating the same calculations for Mo Kα1 radiation ( = 0.7093171 Å), we find that the
Mo Kα1 photon energy is 17.48 keV.
Copyright © 2009 by Springer 35
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. You are in charge of buying a new powder diffractometer for your company. The company is
in business of manufacturing alumina (Al2O3) based ceramics. The powder diffractometer
will become a workhorse instrument in the quality control department. Routine experiments
will include collecting powder diffraction data from ceramic samples to analyze their
structure and phase composition. High data collection speeds are critical because a typical
daily number of samples to be analyzed using the new equipment is 100+. The following
options are available from different vendors:
Sealed Cu X-ray tube, scintillation detector; the lowest cost.
Sealed Cu X-ray tube, solid state detector; $10,000 more than the first option.
Sealed Cu X-ray tube, curved position sensitive detector; $25,000 more than the first option.
What recommendation will you make to you boss without a fear of being fired during the first
month after the delivery of the instrument?
Solution
Since the speed of data collection is the most important issue (480 minute workday leaves
less than 5 min per sample), the smartest decision would be to suggest buying the most
expensive system with a curved position sensitive detector. It offers the fastest data collection
speeds, and therefore, improved productivity. A single experiment can be completed in as
little as a few minutes. Resolution may suffer a bit, but alumina-based materials are well
known, and therefore, some loss of resolution is acceptable for the application sought.
Copyright © 2009 by Springer 36
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 7
1. A student prepares a sample and collects a powder diffraction pattern on an instrument that is
available in the laboratory overseen by his major professor. The student then takes the same
sample to a different laboratory on campus and collects a second pattern. When the student
comes back to his office, he plots the two patterns. The result is shown in Figure 28.
Analyze possible sources of the observed differences.
500
400
Intensity, Y (arb. units)
300
200
100
0
25 30 35 40 45
Bragg angle, 2 (deg.)
Figure 28. Two powder diffraction patterns collected by a student using the same sample but two
different powder diffractometers.
Solution
The differences are in the intensities of the observed peaks, which appear to be approximately
twice as high in one pattern compared to the other. Considering Eq. 7.7 and recalling that the
same sample was used in both experiments, the observed differences may only originate from
the scale factor K. It is possible that two diffractometers were providing different intensities
(fluxes of photons) in the primary beam reaching the sample or reaching the detector. It is
also possible that for whatever reason, different volumes of the sample were producing the
corresponding diffraction pattern. It is also possible that both factors (incident photon flux
and diffracting volumes) were different. Another (though remote) possibility is that quantum
efficiency of two detectors (nothing is known about what kinds of detectors were used in the
two experiments) was different.
Copyright © 2009 by Springer 37
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. The following is the list of five longest interplanar distances possible in a crystal lattice of
some material: 4.967, 3.215, 2.483, 2.212, and 1.607 Å. Calculate Bragg angles (2θ) at
which Bragg reflections may be observed when using Cr Kα1 or Cu Kα1 radiation.
Solution
According to the Braggs’ law, 2dsinθ = λ. Hence, 2θ = 2arcsin(λ/2d).
For Cr Kα1 radiation, λ = 2.28975 Å, and the following is the list of the Bragg angles
corresponding to the five listed interplanar distances:
26.65º, 41.72º, 54.91º, 62.34º, and 90.87º.
For Cu Kα1 radiation, λ = 1.5405929 Å, and the following is the list of the Bragg angles
corresponding to the five listed interplanar distances:
17.84º, 27.73º, 36.15º, 40.76º, and 57.28º.
Copyright © 2009 by Springer 38
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. Researcher finished collecting a powder diffraction pattern of an unknown crystalline
substance. She used Cu Kα radiation, =1.54178Å. The first Bragg peak is observed at
o
2θ = 9.76 . Based on this information she makes certain conclusions regarding the length of
at least one of the three unit cell edges. What are these conclusions?
Solution
From the Braggs equation: d = 9.062 Å. This represents the shortest observed reciprocal
lattice vector.
Assuming that this vector has the simplest possible indices (001, 010 or 010), the
corresponding lattice parameter (a, b, or c, respectively) is 9.062 Å. Considering the
possibility of doubling, tripling, etc. of the non-zero index, the lattice parameter may also be
18.124 Å, 27.186 Å, etc.
Assuming that this vector has only one or none zero indices, the lattice parameter is greater
than 9.062 Å.
Hence, the conclusion by the researcher is that one of the lattice parameters of the material is
greater or equal to 9.062 Å.
Copyright © 2009 by Springer 39
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 8
1. Vanadium oxide, V2O3, crystallizes in the space group symmetry R3c with lattice parameters
a = 4.954 Å and c = 14.00 Å. Calculate the interplanar spacing, d, and Bragg peak positions,
2, for the 104 (the strongest Bragg peak) and for the 012 (the lowest Bragg angle peak)
reflections assuming Cu K1 radiation with = 1.5406 Å.
Solution
Since the crystal system is rhombohedral with hexagonal basis, we will use Eq. 8.4:
1 4 h 2 hk k 2 l 2
2
d2 3 a2 c
to calculate the corresponding interplanar distances and Bragg angles in combination with
Braggs’ equation:
1 4 12 42
104: 0.13596 d 2.7120 Å; 2 = 33.00
d 2 3 4.954 2 14.00 2
1 4 12 22
012: 0.07474 d 3.6578 Å; 2 = 24.31
d 2 3 4.954 2 14.00 2
Copyright © 2009 by Springer 40
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. A powder diffractometer (R = 240 mm) that you used recently is well maintained. However,
the powder diffraction pattern you collected shows some systematic deviations between the
calculated and observed positions of Bragg peaks. You plotted the corresponding deviations
(Δ2θ = 2θobs - 2θcalc) versus different functions of the Bragg angle, two of which are shown in
Figure 29. Which factor is primarily responsible for the observed deviations? Estimate the
value of the corresponding physical parameter that systematically affects peak positions.
-0.060 -0.060
-0.065 -0.065
-0.070 -0.070
2 (deg.)
2 (deg.)
-0.075 -0.075
-0.080 -0.080
-0.085 -0.085
-0.090 -0.090
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 0.70 0.75 0.80 0.85 0.90 0.95 1.00
sin2 cos
Figure 29. Deviations between 2θobs - 2θcalc plotted as functions of sin2θ (left) and cosθ (right).
Solution
The plot on the right is linear. According to Eq. 8.13, this is a strong indication that the major
systematic error comes from sample displacement. The estimation of the slope is shown in
Figure 30 (right).
-0.060 -0.060
-0.065 -0.065
-0.070 -0.070
2 (deg.)
2 (deg.)
-0.075 -0.075
-0.080 -0.080
-0.085 -0.085
-0.090 -0.090
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 0.70 0.75 0.80 0.85 0.90 0.95 1.00
sin2 cos
Figure 30. Deviations between 2θobs - 2θcalc plotted as functions of sin2θ (left) and cosθ (right). The
estimated values of two data points on the straight line are (0.75, -0.0645) and (0.95, -0.082).
The slope of the curve is (-0.0645º – -0.082º)/(0.75-0.95) = -0.088º. Considering Eq. 8.18,
p5 = -2s/R (radians)
Thus, sample displacement, s = -Rp5/2/57.296 = 2400.088/2/57.296 0.18 mm.
Copyright © 2009 by Springer 41
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. What is the multiplicity factor for reflections hkl in the monoclinic crystal system in a
standard setting? How about reflections h0l and 0kl? Do the multiplicity factors change for
the same groups of Bragg reflections in the second allowed setting in the monoclinic crystal
system (i.e. when the non 90º angle changes from β to )?
Solution
Consider the projection of a standard monoclinic reciprocal lattice along b*, which is shown
in Figure 31.
c*
m
a*
Figure 31. The projection of a monoclinic reciprocal lattice along b*. The red points are hkl or h0l. The
blue points are 00l and 0kl.
Any point hkl (red) has a total of four symmetrically equivalent points: hkl above the plane of
the paper, h-kl below, -hk-l above, and -h-k-l below. Thus, the multiplicity factor for the hkl
reflections is 4.
Any point h0l (red) is located in the plane of the paper. Hence, only two are equivalent: h0l
and -h0-l. The corresponding multiplicity factor is 2.
Points 0kl (blue) have the following equivalents: 0kl (above), 0-kl (below), 0k-l (above), and
0-k-l (below). The corresponding multiplicity factor is 4.
In the second allowed setting, where the unique two-fold axis is parallel to Z, the c* and b*
axes are interchanged. Correspondingly, the multiplicity factor is 4 for hkl, h0l, and 0kl
reflections.
Copyright © 2009 by Springer 42
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
4. A powder diffractometer in your laboratory is equipped with a sealed X-ray tube, which has
Cr anode. You need to design a -filter to ensure that the intensity of the K spectral line is
less than 0.5% of the intensity of the K1 part in the characteristic spectrum. Calculate the
needed thickness of a foil made from the most appropriate element (which one?) and by how
much the intensity of K1 and K lines will be reduced after filtering.
Solution
Considering Table 8.3 we find that the most appropriate -filter material to selectively absorb
the K component in the characteristic spectrum emitted by Cr-anode is V. Its mass
absorption coefficients are 96.5 and 479 cm2/g for Cr K and Cr K energies, respectively.
The gravimetric density of V is 6.11 g/cm3 (the value is available in any metals’ handbook;
multiple sources listing basic properties of chemical elements are readily available on the
Web, e.g. see http://www.webelements.com/)
Using Eq. 8.49, the following are the corresponding linear absorption coefficients:
(K) = 96.56.11 = 589.6 cm-1
(K) = 4796.11 = 2927 cm-1
The desired intensity ratio is IK/IK = 200/1. Thus, using Eq. 8.50 and solving it with
respect to x we easily find the necessary thickness of a -filter made from metallic V:
I K exp μ α x ln 40
5 x x 1.58 10 3 cm
I K exp μ β x μ μα
Knowing the thickness of the -filter, the reductions of intensity are determined from Eq.
8.50:
K: exp(-589.60.00158) = 0.394 (transmitted fraction); IK is reduced by a factor of 2.54.
K: exp(-29270.00158) = 0.00981 (transmitted fraction); IK is reduced by a factor of 102.
Note, that IK:IK before filtering is 5:1 and therefore, (5/2.54):(1/102) results in ~200:1.
Copyright © 2009 by Springer 43
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. Increasing the distance between the X-ray source and the sample and between the sample and
the detector improves the resolution of a powder diffraction pattern. However, absorption of
X-rays by air is non-negligible, and increasing these distances usually results in the reduction
of registered intensity. In order to minimize absorption by air, researcher considers installing
two waveguides – tubes filled with hydrogen gas at 0.5 atm – one along the path of the
incident beam, and another along the path of the scattered beam. Each waveguide is capped
with a pair of 0.1 mm thick Be windows. Schematic of the modifications is shown below.
Waveguides filled
Source with H2 at 0.5 atm
Detector
Be windows
Sample
Figure 32. The schematic of a modified powder diffractometer in which both the primary and scattered
beams pass through the waveguides filled with hydrogen at PH2 = 0.5 atm.
Assume that X-ray data are collected using Cu K radiation at room temperature (20 °C) and
normal atmospheric pressure (1 atm) and that the length of each tube is 250 mm. Assume
that air is 20 mass % oxygen and 80 mass % nitrogen.
a) Compute intensity gain, if any, after the installation of the tubes.
b) What is the required minimum length of each tube to gain intensity?
Find all missing physical quantities using the textbook, relevant handbooks, and/or the web.
Solution
Mass absorption coefficients: H: 0.391 cm2/g
N: 7.44 cm2/g
O: 11.5 cm2/g
Be: 1.01 cm2/g
Density Be: 1.85 g/cm3
a) For a single waveguide:
Two Be windows: = 1.011.85 = 1.87 cm-1; I = I0e-x = I0e-1.870.02=0.963I0
H2: at 293 K, 0.5 atm: 2/22400/2273/293 = 4.159610-5 g/cm3
= 0.3914.159610-5 = 1.626410-5cm-1; I = I0e-x = I0e-0.00001626425=0.999I0
Be+H2: I = 0.9990.963I0 = 0.962I0
2 waveguides:
I = 0.9620.962I0 = 0.925I0
Air:
at 293 K, 1 atm: 29/22400273/293 = 1.20610-3 g/cm3
/ = 0.211.5 + 0.87.44 = 8.252 cm2/g
Copyright © 2009 by Springer 44
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
= 8.2521.20610-3 = 9.95210-3 cm-1
I = I0e-x = I0e-0.00995250 = 0.608I0
Intensity gain:0.925/0.608 = 1.521 = 52.1%
b) The minimum length of the tube (y) to gain intensity can be found from the following
inequality
I0e-0.009952y > I0e-1.870.02 e-0.000016264(y-0.02) → e-0.009952y > e-(1.870.02+0.000016264(y-0.02))
which is easily solved with respect to y:
y > 3.76 cm
Copyright © 2009 by Springer 45
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 9
1. A student collected a powder diffraction pattern from an organometallic compound on a
standard powder diffractometer equipped with a sealed Cu Kα X-ray tube. She noticed that
scattered intensity decays rapidly and she can not see any Bragg peaks beyond 2θ = 60º. Her
goal is to have reliable intensities at 90º+ of 2θ. She thinks for a minute and then calls the
crystallography lab at her university to schedule time on one of their units. The lab has three
powder diffractometers, all equipped with Cu Kα X-ray tubes: a rotating anode unit operating
at ambient environment, and two sealed tube units, one with a cryogenic attachment (the
lowest temperature is 77 K) and another with a furnace (the highest temperature 1,100 K).
Time on which unit the student asked for and why?
Solution
Considering Eq. 9.3, the temperature factor is strongly affected by temperature. As
temperature increases, lattice vibrations increase too, and the temperature factor (see Eq. 9.5
and Figure 9.2) will lead to a more rapid suppression of the structure factors (and Bragg
intensities) with increasing sinθ/λ. Hence, to uniformly raise the structure factors at higher
Bragg angles, one needs to lower the temperature. This is why the student asked for time on
the unit equipped with a cryogenic attachment.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Consider Figure 10.1 in Chapter 10, which shows powder diffraction patterns collected from
the same material (CeRhGe3) at room temperature (T 295 K) using X-rays and at T = 200 K
using neutrons. Setting aside differences between intensities of individual Bragg peaks, the
most obvious overall difference between the two sets of diffraction data is that diffracted
intensity is only slightly suppressed towards high Bragg angles (sinθ/λ) in neutron diffraction,
while it is considerably lower in the case of X-ray data. Can you explain why?
Solution
The normal atomic scattering factor in X-ray diffraction decreases as sinθ/λ increases, and
therefore, the structure factors are uniformly reduced. On the other hand, the coherent
scattering length in neutron diffraction is independent of sinθ/λ, which explains higher
scattered intensity at high Bragg angles. Another minor factor is temperature difference:
lowering temperature lowers displacement parameters of all atoms, thus also helping to
increase scattered intensity at high sinθ/λ.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. Establish which combinations of indices are allowed and which are forbidden in the space
group symmetry Cmc21. List symmetry elements that cause each group of reflections to
become extinct?
Solution
Using the information listed in Tables 9.1-9.3 and Table 9.6, the following combinations of
indices are allowed and forbidden:
Reflection type Allowed Forbidden Responsible symmetry element(s)
hkl and hk0 h + k = 2n h + k = 2n +1 base-centered lattice
h0l and h00 h = 2n h = 2n +1 base-centered latticea
h0l l = 2n l = 2n +1 glide plane c Y
0kl and 0k0 k = 2n k = 2n +1 base-centered latticea
00l l = 2n l = 2n +1 glide plane c Y b and screw axis 21 || Z
a
derivative from the first condition.
b
derivative from the third condition.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
4. Powder diffraction pattern of a compound with unknown crystal structure was indexed with
the following unit cell parameters (shown approximately): a = 10.34 Å, b = 6.02 Å, c = 4.70
Å, = 90, = 90 and = 90. The list of all Bragg peaks observed from 15 to 60° 2 is
shown in Table 1. Analyze systematic absences (if any) present in this powder diffraction
pattern and suggest possible space groups symmetry for the material.
Table 1. List of Bragg peaks with their intensities and indices observed in a powder diffraction pattern
of a material indexed in the following unit cell: a = 10.34 Å, b = 6.02 Å, c = 4.70 Å and = 90, =
90 and = 90.
h k l I/I0 2° h k l I/I0 2°
2 0 0 255 17.105 2 0 2 207 42.154
1 0 1 583 20.712 3 2 1 59 44.296
2 1 0 207 22.629 2 1 2 47 44.899
0 1 1 77 23.966 4 2 0 19 46.246
1 1 1 741 25.495 5 0 1 17 47.978
2 0 1 120 25.572 0 2 2 133 49.120
2 1 1 665 29.598 0 3 1 15 49.339
0 2 0 106 29.650 1 2 2 28 49.961
3 0 1 327 32.152 1 3 1 123 50.166
2 2 0 23 34.448 5 1 1 68 50.470
3 1 1 1000 35.518 2 2 2 332 52.407
1 2 1 317 36.451 4 0 2 332 52.407
4 1 0 204 37.813 2 3 1 132 52.595
1 0 2 116 39.242 4 1 2 160 54.879
2 2 1 139 39.550 6 1 0 195 55.369
4 0 1 169 39.723 3 3 1 241 56.506
1 1 2 207 42.154 4 3 0 143 58.128
Solution
The crystal system is orthorhombic. Thus, we should use Table 9.6 to establish possible space
groups. For all observed reflections found in Table 1: 0kl, k + l = 2n; hk0, h = 2n;
h00, h = 2n; 0k0, k = 2n; 00l, none found (even though none reflections of this type are seen,
the condition must be l = 2n, which is derivative of 0kl, k + l = 2n). Possible space groups
symmetry are Pnma and Pn21a (Pna21 in standard setting with b and c axes switched).
Copyright © 2009 by Springer 49
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. Powder diffraction pattern of a compound with an unknown crystal structure was indexed
with the following unit cell parameters: a = b = 4.07 Å, c = 16.3 Å, = = 90, =120. The
list of all Bragg peaks observed from 2 to 120° 2 is shown in Table 2. Analyze systematic
absences (if any) present in this powder diffraction pattern and suggest possible space groups
symmetry for the material.
Table 2. List of Bragg peaks with their intensities and indices observed in a powder diffraction pattern
of a material indexed in the following unit cell: a = b = 4.07 Å, c = 16.3 Å, = = 90, =120
h k l I/I0 2° h k l I/I0 2°
0 0 3 10000 18.541 0 1 -10 159 75.324
0 1 -1 8851 34.192 0 2 4 256 76.249
0 1 2 280 35.927 0 2 -5 62 79.293
0 0 6 156 37.629 0 0 12 122 80.452
0 1 -4 4599 42.243 0 1 11 159 82.405
0 1 5 817 46.517 0 2 7 572 87.346
0 1 -7 3157 56.682 1 1 9 1097 88.383
0 0 9 1389 57.905 0 2 -8 1045 92.316
1 1 0 3322 60.143 1 2 -1 534 100.328
0 1 8 5186 62.442 1 2 2 59 101.427
1 1 3 456 63.511 1 2 -4 164 105.431
0 2 1 832 71.064 0 0 15 200 107.679
0 2 -2 136 72.107 1 1 12 189 109.601
1 1 6 206 73.182 1 2 -7 439 117.229
Solution
The crystal system is hexagonal, trigonal or rhombohedral. Thus, we should use Table 9.7
and Table 9.8 to establish possible space groups. For all reflections, present in Table 2:
hkl, -h + k + l=3n; h0l, -h + l=3n; h00, -h =3n; 00l, l=3n. General reflections (hkl) all
have -h + k + l=3n, which points to a rhombohedral lattice and eliminates hexagonal crystal
system. Thus, possible space groups are R3, R32, R, R3m or Rm (Table 9.7).
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6. At room temperature the lanthanide material cerium (Ce) has a face centered cubic crystal
structure, which is known as -Ce. The space group is Fmm and the lattice parameter
a=5.161 Å. When cooled below 77 K it transforms to -Ce, which also has a face centered
cubic crystal structure (space group Fmm) with the lattice parameter a=4.85 Å.
a) Calculate Bragg angles (2θ) for all Bragg peaks that may be observed between 0 and 100o
2θ using Cu K radiation =1.54178 Å for both - and -Ce.
b) Sketch diagrams of both diffraction patterns indicating only the positions of possible
diffraction peaks.
c) Discuss the differences between the two diffraction patterns (if any) you expect to see
when the actual diffraction patterns are collected.
Solution
High-temperature -Ce, a = 5.161 Å Low-temperature -Ce, a = 4.85 Å
h k l 2θº h k l 2θº
1 1 1 29.963 1 1 1 31.934
0 0 2 34.735 0 0 2 37.041
0 2 2 49.940 0 2 2 53.387
1 1 3 59.341 1 1 3 63.572
2 2 2 62.265 2 2 2 66.758
0 0 4 73.311 0 0 4 78.882
1 3 3 81.169 1 3 3 87.623
0 2 4 83.744 0 2 4 90.514
2 2 4 93.970
-Ce -Ce
20 30 40 50 60 70 80 90 100 20 30 40 50 60 70 80 90 100
Bragg angle, 2 (deg.) Bragg angle, 2 (deg.)
Figure 33. Calculated positions of Bragg peaks that are possible in -Ce (left) and -Ce (right).
Given the expected identical distribution of atoms in both unit cells, the most significant
difference will be the shift of Bragg reflections towards higher Bragg angles in -Ce when
compared to -Ce. One Bragg reflection exceeds 100o due to this shift. Some increase in
relative intensities at high Bragg angles may be expected due to the reduction of temperature,
which reduces atomic displacement parameter and enhances intensity scattered at high Bragg
angles.
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Chapter 10
1. A material crystallizes in space group symmetry Cmmm. After deconvoluting a powder
diffraction pattern collected from this material, a student computes the Patterson function. He
finds out that two strongest peaks in the Patterson function have different coordinates (0,0,0
and ½,½,0) but identical heights. Is this result expected, or was there some kind of an error
made in his computations?
Solution
There were no errors in the computations. In the Patterson function, all of the interatomic
vectors begin in the origin of coordinates (0,0,0) leading to this peak being the strongest. In
the base centered lattice C, every atom in the structure has a symmetrically equivalent atom
shifted by the corresponding lattice translation, (½,½,0). Hence this peak must be identical in
strength (height) to that in the origin of coordinates. Another way to solve the problem is to
check the corresponding symmetry of the Patterson function in the International Tables for
Crystallography. It is Cmmm, hence the points (0,0,0) and (½,½,0) are symmetrically
equivalent in the Patterson function space.
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2. A total of 16 reflections have been chosen as a basis set for a direct phase determination
attempt. Knowing that the crystal structure is centrosymmetric with none of the atoms
scattering anomalously, calculate how many different unrestricted combinations of phases in
the basis set will be tested when computations are completed.
Solution
Since the crystal structure is centrosymmetric with all atoms scattering normally, then each
reflection in the basis set may have the following phases: 0 or π. For one reflection in the
basis set, the total number of possibilities is 2 (0 or π). For a two-reflection basis set the
following is an exhaustive list of possibilities: 00, π0, 0π, and ππ. For a three-reflection basis
set, the number of combinations becomes 8: 000, π00, 0π0, 00π, ππ0, π0π, 0ππ, and πππ. It is
easy to deduce that in general, the number of possible combinations is 2N, where N is the
number of reflections in the basis set. For a 16-reflection basis set the total of 216=65536
combinations of phases will be tested.
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Chapter 11
1. There are 25 plates in a Soller slit. Axial size of the incident beam when it exits the slit is 12
mm. Calculate the length of the plates along the X-ray beam (l) if the slit results in the axial
divergence of the beam, = 2.5°. Neglect the thickness of the plates.
Solution
Consider Figure 11.8, which illustrates how the plates are arranged in a Soller slit. Since there
are 25 plates and the size of the beam in the direction perpendicular to the plates is 12 mm,
the distance between each plate is d = 12/24 = 0.5 mm. Using Eq. 11.2, the length of the
plates (l) is
360d
l 23 mm
απ
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2. A crystal monochromator is made form high quality pyrolitic graphite (space group P63/mmc,
a = 2.464, c = 6.711 Å). Assume that this crystal is used to suppress the K2 spectral line of
Cu K radiation by using the reflection from (002) planes and that the crystal is cleaved
parallel to the (001) plane. Estimate the linear separation (, in mm) between the centers of
two Bragg peaks (K1 and K2) at 200 mm distance after the reflection from the crystal.
Assuming that the crystal is nearly ideal calculate angle which the incident beam should
form with the surface of the crystal for best result.
Solution
The interplanar distance, d, for the (002) planes of a pyrolitic graphite is 6.711/2 = 3.3555 Å.
Using the Braggs’ equation and the wavelengths listed in Table 6.1, the centers of the K1
and K2 reflections should be observed at
1.54059
K1: arcsin 13.271
2 3.3555
1.54441
K2: arcsin 13.305
2 3.3555
The angular separation (13.305 – 13.271 = 0.034o) can be easily converted into the linear
separation, , at a distance, l = 200 mm, using the following expression:
2
l 0.12 mm
360
The best result is expected when the surface of the crystal forms an angle = 13.271o with
the incident beam, i.e. exactly matches the ideal reflecting position for the K1 component.
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3. Two powder diffraction patterns (Figure 34) were collected from the same material. The first
experiment was carried out at elevated temperature and the second at room temperature. The
high temperature crystal structure is cubic with the indices of Bragg reflections as marked.
Note that a small amount of an impurity phase is also present, as can be concluded from three
weak unindexed Bragg peaks observed approximately at 18º, 26º and 32º of 2θ. What
happens when the sample is cooled to room temperature? What can you tell about the crystal
structure of the majority phase at room temperature?
40
011
35
Mo K radiation
Observed intensity, Y (counts)
30
25
20
15 112
002
111
10
003, 122
022
001 013 222 123
5 012 HT
113 RT
023
0
10 15 20 25 30 35 40
Bragg angle, 2 (deg.)
Figure 34. Powder diffraction patterns of a material collected at room temperature (RT) and elevated
temperature (HT) using Mo K radiation.
Solution
At room temperature, many of the Bragg peaks that belong to the majority phase become
broader or split. Nothing obvious happens to the Bragg peaks of the minority phase. Based
on this observation it is possible to conclude that the majority phase undergoes a structural
transformation on cooling, while the minority phase does not change its structure.
By analyzing the indices of Bragg peaks which appear to remain unchanged and those that
broaden or split, it is possible to deduce what type of a structural distortion occurs in the
majority phase.
HT RT
001 Appears to be slightly broader
011 No visible change
111 No visible change
002 Splits at least in two
012 Splits at least in two
112 Splits at least in two
022 Splits at least in two
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003,122 Splits at least in two
013 Splits at least in two
113 Splits at least in two
222 No visible change
023 Broadens, likely splits but not enough data to make a decision
123 Splits at least in two
What is clear is the following:
Bragg reflections 111 and 222 remain unchanged (likely all hhh are unchanged)
Bragg reflections 001 (broadens) and 002 (splits into two)
Based on this, it is likely (but not necessarily true) that the symmetry of the majority phase
lowers from cubic to tetragonal (001 becomes 010 and 001; 002 becomes 020 and 002; 111
and 222 remain unaffected by the distortion). The actual powder diffraction pattern, and not
only the plot shown in Figure 34, should be analyzed to arrive to a final conclusion because
the distortion may be from the cubic to the orthorhombic, monoclinic, or even triclinic crystal
system.
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Chapter 12
1. Assume that you are to collect powder diffraction data from a powder with the purpose to
establish and refine its crystal structure. Earlier, you have used powder diffractometer:
A) Sealed X-ray source, curved position sensitive detector, the radius of its goniometer is
150 mm and diffraction data are collected in the transmission mode using cylindrical
specimens. You employed this equipment to characterize the phase purity of your
material. In addition to this device, other departments at your university have the
following powder diffractometer systems:
B) Sealed X-ray tube source, Bragg-Brentano goniometer, radius 185 mm, scintillation
detector.
C) Rotating anode source, Bragg-Brentano goniometer, radius 285 mm, scintillation
detector.
D) Sealed X-ray tube source, Bragg-Brentano goniometer, radius 250 mm, cooled solid-state
detector.
Establish the order in which you would call people in charge of the diffractometers to arrange
for data collection, and explain why.
Solution
Your goal is to obtain the highest quality data for structure solution and refinement. Based on
this, the order of your calls should be as follows:
C: Rotating anode source, Bragg-Brentano goniometer, radius 285 mm, scintillation detector.
This combination ensures high intensity (rotating anode) and highest resolution (largest
radius and scintillation detector).
D: Sealed X-ray tube source, Bragg-Brentano goniometer, radius 250 mm, cooled solid state
detector. This combination ensures high intensity (cooled solid state detector) and next best
resolution (large radius and a point detector).
B: Sealed X-ray tube source, Bragg-Brentano goniometer, radius 185 mm, scintillation
detector. This combination gives lower intensity (scintillation detector) and lower resolution
(even a smaller radius but still a point detector).
A: Sealed X-ray tube source, cylindrical sample, radius 150 mm, curved position sensitive
detector. This combination gives lowest resolution (smallest radius and position sensitive
detector). However, intensity data may be of excellent quality provided your sample is not X-
ray fluorescent.
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2. Now assume that you have 20 different samples to characterize with respect to their phase
composition. Furthermore, each department charges $50.00 per hour for the use of their
equipment (the money goes to a special account, which pays for a service contract and
routine maintenance). Assuming the availability of the same diffractometers as in Problem 1,
what would be the order on your calling list and why?
Solution
Your goal is to obtain decent quality data for phase identification in the shortest time (which
translates into a minimum cost). Based on this, the order of your calls should be as follows:
A: Sealed X-ray tube source, cylindrical sample, radius 150 mm, curved position sensitive
detector. This combination gives the lowest resolution (smallest radius and position sensitive
detector) but the highest intensities in the shortest time.
C: Rotating anode source, Bragg-Brentano goniometer, radius 285 mm, scintillation detector.
This combination ensures high intensity (rotating anode) and high resolution (largest radius
and scintillation detector). The data can be collected in a few hours provided you use quick
scans at 5-10 deg/min.
D: Sealed X-ray tube source, Bragg-Brentano goniometer, radius 250 mm, cooled solid state
detector. This combination ensures high intensity (cooled solid state detector) and next best
resolution (largest radius and point detector). The data can be collected reasonably quickly.
B: Sealed X-ray tube source, Bragg-Brentano goniometer, radius 185 mm, scintillation
detector. This combination gives the lowest intensity (scintillation detector) and low
resolution (even smaller radius but still a point detector). You will spend longest time on data
collection employing this diffractometer.
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3. When you called the person in charge of the diffractometer D (see Problem 1) she told you
that the goniometer axis is horizontal and that the X-ray source arm is stationary. Do you
need to worry about mixing your powder with a binder?
Solution
Generally yes, especially when experimental data will be collected at high Bragg angles
because the sample holder tilts. Thus, at 2= 90o, the sample surface will be tilted at 45o
with respect to the horizon (see the figure below) and the powder may spill out of the holder
if not mixed with a binder.
2
F
Figure 35. Expected position of the flat sample at 2= 90o during data collection.
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4. When preparing for the experiment described in problem 1 you used mortar and pestle to
grind the sample. You were completely satisfied with the result since the powder appeared
fine and homogeneous to your eyes, but when you discussed the process with your thesis
advisor, she asked you to screen the powder through a 25 m sieve. This discussion happened
just before you were about to take off across campus since your allotted time on the powder
diffractometer starts in 10 minutes. Describe your course of action and explain why?
Solution
(a) – Call the person in charge of the diffractometer and inform her that you will be late since
you have to screen the powder. Sifting the powder brakes agglomerates and eliminates large
particles, thus improving the quality of the resulting powder diffraction pattern.
(b) – Take the screen with you and sift the powder before mounting it on a holder at the
expense of allotted time. It is always better to prepare the sample to the best of your ability
rather than later find out that the quality of your experimental data is unsuitable for the
refinement. If this will be the case, your advisor will likely ask you to redo the experiment
anyway as soon as she finds out that you did not take every step to ensure the best quality of
data.
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5. You made a flat sample in the preparation for a highly accurate powder diffraction
experiment using diffractometer D (see Problem 1). The sample completely fills a cylindrical
opening 25 mm in diameter (d). The lowest Bragg angle during the experiment will be 2 =
10o. The set of divergence slit available on this instrument includes the following apertures:
0.05, 0.1, 0.25, 0.5, 0.75, 1, 2, and 5 mm. Knowing that the distance between the focus of the
X-ray tube and the divergence slit is 60 mm, select the most appropriate divergence slit to be
used in your experiment and explain why?
Solution
The maximum acceptable angular divergence of the slit ():
R d sin 25 sin 5
d 0.0087 radians 0.5o
sin R 250
180 D S
Using ) and recalling that the typical S is 0.1 mm (see Figure 11.7), we
L
find that the opening of the divergence slit, D, must be smaller than 0.425 mm. The most
appropriate divergence slit, is therefore, 0.25 mm.
Since the size of the cathode projection is not specified in the problem statement, it may be
necessary to verify this estimate by placing a fluorescent screen instead of a sample in the
sample holder to visually ensure that the projection of the X-ray beam is shorter than the
sample length at the lowest Bragg angle in the planned experiment.
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6. You are having difficulties with making a flat sample for a high precision powder diffraction
experiment – the powder just will not spread evenly in a cylindrical hole ~20 mm diameter
and 1 mm deep. You are considering the following options:
a) Compact the powder by pressing a glass slide against the surface of the sample
b) Make a suspension in petroleum ether and pour it into the hole
c) Backfill the holder while the front of the sample is pressed against a glass slide with a
strip of rough sand paper glued to one of its surfaces
d) Use a different sample holder and dust the powder on top.
Arrange these options in the order which should result in the best quality specimen for
powder diffraction and explain why.
Solution
This kind of a problem usually arises when your powder is a low-density material. It implies
that its linear absorption coefficient is quite small. Thus, a thick sample is the best specimen
for a powder diffraction experiment using Bragg-Brentano geometry. The following is the
proper arrangement of the options:
b) Make a suspension in petroleum ether and pour it into the hole. Certainly, if the powder is
soluble in ether, this option is not applicable (test a small amount of your powder for
solubility).
c) Backfill the holder while the front of the sample is pressed against a glass slide with a strip
of rough sand paper glued to one of its surfaces. This procedure will result in a thick
specimen with good homogeneity, flat surface (not considering the roughness created by the
contact with a sand paper), and relatively small induced preferred orientation on the sample
surface.
d) Use a different sample holder and dust the powder on top. This will create a specimen with
low preferred orientation but the homogeneity may be difficult to achieve. Since the sample is
lightweight, this will also create a problem with distorted intensity at high Bragg angles.
a) Compact the powder by pressing a glass slide against the surface of the sample. This is the
worst of four choices because it will inevitably produce a specimen with the highest preferred
orientation.
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7. You were able to arrange time on the powder diffractometer C (see problem 1). Several
sample holders are available:
a) powder fills a cylindrical hole 25 mm diameter and 1 mm deep;
b) powder fills a cylindrical hole 20 mm diameter and 1 mm deep;
c) powder fills a square hole 30301 mm3;
d) powder is dusted on top of a round rough spot 25 mm in diameter.
Arrange these sample holders in the order from the most to the least suitable for a high
precision powder diffraction experiment, and explain why. Assume that you are working with
a molecular compound.
Solution
Linear absorption coefficient is quite small in molecular compounds. Thus, a thick sample is
the best specimen for a powder diffraction experiment using Bragg-Brentano geometry. The
following is the proper arrangement of the options:
c) powder fills a square hole 30301 mm3. Thick sample and the largest area (translates into
the largest possible divergence slit aperture).
a) powder fills a cylindrical hole 25 mm diameter and 1 mm deep. Same as (c) but lower
intensity due to the reduction of the area and the divergence slit aperture.
b) powder fills a cylindrical hole 20 mm diameter and 1 mm deep. Same as (c) and (a) but
lower intensity due to further reduction of the area and the divergence slit aperture.
d) powder is dusted on top of a round rough spot 25 mm in diameter. This is the worst choice
because the sample is low absorbing.
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8. Answer Problem 7 if you are working with an intermetallic compound containing a
lanthanide element:
Solution
Linear absorption coefficient is generally large in intermetallic compounds, especially those
containing lanthanides (La through Lu), which are heavy elements. Thus, sample thickness in
not an issue and only the area of the sample is critical. Hence, (c), then (d) (a), then (b).
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9. You are using Fe K radiation to collect powder diffraction data employing powder
diffractometer C (see problem 1). After several quick scans, you established that the receiving
slit with the aperture of 0.03° results in both acceptable resolution and intensity. Bragg peaks
appear to have a full width at half maximum between 0.4 and 0.5° 2. What is the largest
allowable step during data collection and why?
Solution
The step,2, should be 0.03o of 2θ or less, otherwise some details of peak shapes will be
lost, see Figure 12.28.
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10. You are about to perform a quick scan from 5 to 70° 2 to verify the crystallinity of your
material and to check whether or not the receiving slit is of adequate width. You are planning
for the experiment which will take 10 to 15 min overall. Which scanning mode (step scan or
continuous scan) is the best to accomplish the task and why?
Solution
Continuous scanning mode should be chosen because it will be the fastest way to collect the
data of the same quality.
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11. In the preparation for an overnight experiment, you performed a quick scan, which resulted in
the powder diffraction pattern shown in Figure 36. The receiving slit was narrow, RS = 0.01°.
You are planning to double the receiving slit aperture and your goal is to measure the highest
intensity data point with 1% or better error at the 99.9% confidence level during a step scan.
Estimate the counting time parameter for the upcoming overnight experiment?
Relative intensity, Y (10 counts per second) 10
6
3
0
10 15 20 25 30 35 40 45 50
Bragg angle, 2 (deg.)
Figure 36. The result of a quick scan experiment using a narrow receiving slit to determine correct data
collection parameters for a future overnight experiment.
Solution
Doubling the receiving slit will result in the highest intensity point ~20,000 counts per
second. We need to achieve 1% error or better at 99.9% confidence level. Using Eq. 12.9 we
find that we need to accumulate ~96,000 counts at this point. Thus, counting time should be
5 s or longer.
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12. Assume that the overnight experiment described in Problem 11 is to be performed using the
continuous scanning mode from 8 to 60° 2 with a sampling step 2 = 0.005°. Estimate
both the scanning rate and the time it will take to finish the experiment.
Solution
Using Eq. 12.7 we find the scan rate is 0.06 deg/min or slower. The range to be scanned is
52o, thus the time of the overnight experiment will be ~14.4 h or longer.
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Chapter 13
1. Consider three powder diffraction patterns, which are shown in Figure 37 to Figure 39. For
each pattern select all applicable processing steps and explain your reasoning assuming that
the goal is to produce digitized (reduced) powder patterns for phase identification.
a) Smooth the data (Yes/No/Probably)
b) Eliminate background (Yes/No/Probably)
c) Strip Kα2 contributions (Yes/No/Probably).
8
Metallic alloy, Cu K
7
6
Intensity, Y (102 counts)
0
30 40 50 60 70 80 90
Bragg angle, 2 (deg.)
Figure 37. Powder diffraction pattern collected using a conventional X-ray source.
6
Metal oxide, synchrotron
5
Intensity, Y (104 counts)
0
3 4 5 6 7 8 9 10
Bragg angle, 2 (deg.)
Figure 38. Powder diffraction pattern collected using a synchrotron X-ray source. (Data courtesy of Dr. M.J.
Kramer.)
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7
Zr-based deuteride, neutrons
Intensity, Y (103 counts)
4
0
20 40 60 80 100
Bragg angle, 2 (deg.)
Figure 39. Powder diffraction pattern collected using a reactor-based neutron source. (Data courtesy of Dr.
W.B. Yelon.)
Solution
Powder diffraction data collected from a metallic alloy employing a conventional powder
diffractometer: visual analysis of the pattern indicates considerable broadening of high angle
sides of Bragg reflections above 2 60o. Thus, K2 components are present, even though
Bragg peaks are not fully resolved at 2 90o. Therefore:
a) The data should be smoothed before background elimination and K2 stripping. The
need for smoothing arises because the maximum number of accumulated counts for the
strongest peak is only about 700. The data were likely collected in a fast experiment.
b) The background should be eliminated, even though it is quite low. However, its
contribution may reach as much as ~50% of peak intensity for weak Bragg reflections,
thus K2 stripping will be incorrect without removing the background.
c) The K2 components should be stripped.
Powder diffraction data collected from a metal oxide employing a synchrotron source: since
a synchrotron source was employed, the radiation is monochromatic (no K2 components are
present).
a) It appears that there is no need to smooth the data because the maximum number of
accumulated counts for the strongest peak is about 60,000. The data appear quite precise,
however a final decision about the need for smoothing should be made when the data are
plotted using a nonlinear intensity scale.
b) There is no need to eliminate the background because of (c). Furthermore, even weak
Bragg peaks appear to be well defined because the background is quite low and a signal-
to-noise ratio appears to be excellent.
c) There are no K2 components in the pattern. K2 stripping is not applicable.
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Powder diffraction data collected from zirconium deuteride employing a reactor-based
neutron source: since a neutron source was employed, the radiation was monochromatic.
a) The data should probably be smoothed to improve background removal and Bragg peak
detection.
b) The background should be eliminated to improve detection of weak Bragg peaks.
c) There are no K2 components in the pattern. K2 stripping is not applicable.
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2. A powder diffraction pattern collected from a metallic alloy was processed into two digitized
patterns. The background was eliminated first, as illustrated in Figure 40 and second, as
shown in Figure 41. Assume that in both cases preliminary processing was continued as
follows: K2 components were stripped and Bragg peak positions and intensities were
determined using an automatic peak search. Compare the reliability of thus obtained
digitized patterns and explain your reasoning.
Figure 40. Example of the automatically determined background (thick line at the bottom of the plot shown
using the scale identical to the experimental data).
Figure 41. Example of the background represented by a polynomial (thick line at the bottom of the plot
shown using the scale identical to the experimental data).
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Solution
It appears that automatically determined background is incorrect: at low Bragg angles the
background line does not follow experimental data and visible background humps appear under
the clusters of strong Bragg reflections.
Polynomial representation of the background appears to be quite accurate. Therefore, the
digitized pattern obtained by employing the polynomial background representation is expected to
be considerably more reliable than the pattern after automatic background subtraction.
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3. Consider the powder diffraction pattern shown in Figure 42 and answering Yes/No/Maybe:
Is this pattern suitable for phase identification? Is the material suitable for crystal structure
determination using powder diffraction? Explain your reasoning. What other conclusions (if
any) can be made from a visual analysis of this pattern?
Organo metallic compound, Mo K
40
Intensity, Y (10 counts)
30
2
20
10
0
5 10 15 20 25 30
Bragg angle, 2 (deg.)
Figure 42. Powder diffraction pattern collected from an organometallic compound on a Rigaku TTRAX
powder diffractometer using Mo K radiation. The data were collected in a continuous scanning mode:
scan rate was 5 deg/min, sampling step 0.01°.
Solution
The powder diffraction pattern maybe suitable for phase identification provided several clusters
of low Bragg angle peaks (e.g. below 2 11o) may be decisively deconvoluted using a suitable
profile fitting utility. It may be necessary to collect a better quality pattern.
The material is likely unsuitable for the crystal structure determination because of the insufficient
resolution of the pattern. Thus, intensities of the individual Bragg peaks will be determined with
large errors. Furthermore, a broad halo-like background and a virtual absence of distinct Bragg
reflections above 2 20o signal the presence of an amorphous phase in the sample. This may
also explain a low resolution of the data.
Other conclusions:
The crystal structure appears to be complex, at least its unit cell has a relatively large volume
(first Bragg peak is observed at 2 4o, which is equivalent to d > ~20 Å) and low symmetry
(multiple overlapping Bragg peaks at any Bragg angle range).
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4. Diffraction data (Table 3) were collected from a white ceramic plate. Using the Mineral
Database1 and 3 strongest of the 15 observed peaks identify the material.
Table 3. Digitized pattern representing data collected from a white ceramic plate.
I/I0 2, d, Å I/I0 2, d, Å I/I0 2, d, Å
57 25.556 3.4827 99 57.465 1.6023 9 77.202 1.2346
88 35.125 2.5528 8 61.268 1.5117 7 80.648 1.1903
39 37.747 2.3812 38 66.481 1.4052 8 88.949 1.0995
100 43.324 2.0867 57 68.165 1.3745 10 91.139 1.0787
49 52.514 1.7412 17 76.834 1.2396 20 95.203 1.0431
Solution
Three strongest reflections arranged according to their intensity (in parenthesis, normalized to
1):
2.09(1) 1.60(1) 2.55(0.9)
The following is the candidate for a matching powder diffraction pattern
2.085(1) 2.552(0.9) 1.601(0.8) Corundum, Al2O3
No other potential matches exist. Given that the plate was “white” and “ceramic” small
differences in relative intensities may be disregarded and we conclude that the plate is made
from aluminum oxide.
1
This is a freely accessible database available at http://webmineral.com/X-Ray.shtml.
Copyright © 2009 by Springer 76
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. Diffraction data (Table 4) were collected from a light-blue colored powder. Using the
Mineral Database and 3 strongest of the 15 observed peaks identify the material.
Table 4. Digitized pattern representing data collected from a light-blue colored powder.
I/I0 2, d, Å I/I0 2, d, Å I/I0 2, d, Å
100 12.778 6.9223 4 41.846 2.1570 6 53.388 1.7147
36 25.724 3.4603 10 43.508 2.0784 3 57.955 1.5900
10 33.514 2.6717 3 49.088 1.8543 2 58.613 1.5737
11 36.438 2.4637 3 51.238 1.7815 2 62.381 1.4873
6 39.753 2.2656 3 52.856 1.7307 3 62.764 1.4792
Solution
Three strongest reflections arranged according to their intensity (in parenthesis, normalized to
1):
6.92(1) 3.46(0.36) 2.46(0.11)
The following is the candidate for a matching powder diffraction pattern
6.91(1) 3.457(0.9) 2.462(0.8) Cu2(NO3)(OH)3
The pattern found in the database is the only matching pattern as far as d-spacing is of
concern. Relative observed intensities of the second and third Bragg reflections are lower
than found in the database but they are the second and third strongest observed peaks (likely
preferred orientation in one of the patterns). Furthermore, the examined powder was colored
light-blue, which is typical for Cu2+ compounds. Thus the powder is Cu2(NO3)(OH)3.
Copyright © 2009 by Springer 77
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
6. Diffraction data (Table 5) were collected from a powder containing fluorine. Using the
Mineral Database and 3 strongest of the 15 observed peaks identify the material. Additional
information about the powder: no weight loss has been detected during a thermogravimetric
experiment carried out between ~25 and ~500°C.
Table 5. Digitized pattern representing data collected from a powder containing fluorine. The powder is
stable between room temperature and ~500°C.
I/I0 2, d, Å I/I0 2, d, Å I/I0 2, d, Å
41 25.850 3.4438 68 33.080 2.7057 37 49.555 1.8380
14 28.123 3.1704 26 34.120 2.6256 18 50.743 1.7977
17 29.081 3.0680 26 40.017 2.2512 17 51.554 1.7713
100 31.905 2.8026 29 46.858 1.9372 13 52.288 1.7482
43 32.235 2.7747 14 48.259 1.8842 19 53.154 1.7217
Solution
Three strongest reflections arranged according to their intensity (in parenthesis, normalized to
1):
2.80(1) 2.71(0.68) 2.77(0.43)
The following are the candidates for matching powder diffraction patterns
2.8(1) 2.702(0.6) 2.772(0.55) Fluorapatite, Ca5(PO4)3F
2.814(1) 2.72(0.6) 2.778(0.6) Hydroxylapatite, Ca5(PO4)3(OH)
Two patterns are found in the database. The material contains fluorapatite, Ca5(PO4)3F,
because fluorine is present. The material does not contain hydroxylapatite, Ca5(PO4)3(OH)
because the latter would decompose on heating. Thus, the material is pure fluorapatite,
Ca5(PO4)3F.
Copyright © 2009 by Springer 78
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
7. Diffraction data (Table 6) were collected from a powder containing manganese. Using the
Mineral Database and 3 strongest of the 15 observed peaks identify the material.
Table 6. Digitized pattern representing data collected from a manganese-containing powder.
I/I0 2, d, Å I/I0 2, d, Å I/I0 2, d, Å
100 28.630 3.1153 66 56.560 1.6258 18 72.249 1.3066
52 37.296 2.4090 16 59.275 1.5577 7 86.457 1.1246
13 40.947 2.2022 7 64.736 1.4388 9 93.578 1.0569
15 42.744 2.1137 13 67.136 1.3931 20 100.604 1.0011
5 46.026 1.9703 15 72.125 1.3085 5 102.886 0.9850
Solution
Three strongest reflections arranged according to their intensity (in parenthesis, normalized to
1):
3.12(1) 1.63(0.66) 2.41(0.52)
The following are the candidates for matching powder diffraction patterns
3.11(1) 2.4(0.6) 1.62(0.5) Argutite, GeO2
3.14(1) 1.63(0.5) 2.41(0.5) Pyrolusite, MnO2
Two matching patterns are found in the database. Only one contains manganese. Thus, the
material is pyrolusite, MnO2.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
8. Diffraction data (Table 7) were collected from a two-phase powder containing Mn, Al and O.
Results of mass spectroscopic analysis with respect to all known chemical elements show
that there are no other elements present in concentration exceeding 100 parts per million by
weight. Using the Mineral Database and 6 strongest of the 13 observed peaks identify both
compounds that are present in the mixture.
Table 7. Digitized X-ray diffraction pattern representing data collected from a two-phase powder
containing Al, Mn and O.
I/I0 2, d, Å I/I0 2, d, Å I/I0 2, d, Å
33 25.460 3.4956 13 40.947 2.2022 66 56.560 1.6258
100 28.630 3.1153 15 42.744 2.1137 58 57.379 1.6045
52 35.031 2.5594 59 43.233 2.0909 16 59.275 1.5577
52 37.296 2.4090 5 46.026 1.9703
23 37.654 2.3869 29 52.426 1.7439
Solution
Six strongest reflections arranged according to their intensity (in parenthesis, normalized to
1):
3.12(1) 1.63(0.66) 2.09(0.59) 1.61(0.58) 2.56(0.52) 2.41(0.52)
The following are the candidates for matching powder diffraction patterns with the strongest
peak at d = 3.12:
3.11(1) 2.4(0.6) 1.62(0.5) Argutite, GeO2
3.14(1) 1.63(0.5) 2.41(0.5) Pyrolusite, MnO2
The remaining three strongest peaks have the following matching patterns:
2.085(1) 2.552(0.9) 1.601(0.8) Corundum Al2O3
Given the chemical composition of the powder, it is a mixture of pyrolusite, MnO2, and
corundum, Al2O3.
Copyright © 2009 by Springer 80
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapter 14
1. Consider the X-ray powder diffraction pattern of LaNi11.6Ge1.4 shown in Figure 43 and found
in the file Ch14Pr01_CuKa.xy online. A total of 27 individual Bragg peaks are measurable
up to 2 = 91°. They are listed in Table 8 and also found in the file Ch14Pr01_CuKa.pks
online. Peak positions, intensities, and full widths at half maximum have been determined
using a profile fitting procedure. The observed Bragg angles are listed for the K1 component
in the doublet, = 1.540593 Å.
a) Using a spreadsheet perform indexing of the powder diffraction pattern assuming cubic
crystal system.
b) Analyze the combinations of Miller indices of the observed reflections, and determine
possible space groups of the material.
c) Using the average value of the lattice parameter calculate both FN and M20 figures of
merit for your indexing result. Is the determined unit cell realistic?
d) Perform least squares refinement of the unit cell parameter using Eq. 14.40 and a
spreadsheet (do not use any freely or commercially available software). Note, that the
normal equation matrix for the case of a single parameter is a single number.
LaNi11.6Ge1.4, Cu K
4
Intensity, Y (10 counts)
3
3
0
10 20 30 40 50 60 70 80 90
Bragg angle, 2 (deg.)
Figure 43. The X-ray powder diffraction pattern of LaNi11.6Ge1.4 collected on an HZG-4a powder
diffractometer using Cu K radiation. Numerical data are available in the file Ch14Pr01_CuKa.xy online.
(Data courtesy of Dr. L.G. Akselrud.)
Copyright © 2009 by Springer 81
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Table 8. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the LaNi11.6Ge1.4 powder diffraction pattern collected using Cu K radiation in the
range 11 2 91° (see Figure 43). Numerical data are found in the file Ch14Pr01_CuKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
33 15.561 0.165 47 70.133 0.119
31 22.099 0.128 25 71.796 0.130
87 27.131 0.122 11 72.343 0.118
80 31.423 0.116 23 74.542 0.119
487 35.255 0.104 127 76.172 0.132
847 38.745 0.100 4 76.691 0.132
1000 47.232 0.114 3 78.887 0.132
191 47.945 0.114 97 80.467 0.128
228 50.716 0.105 147 83.114 0.141
86 55.950 0.116 32 85.233 0.138
172 58.455 0.117 158 87.336 0.151
194 60.890 0.118 65 88.909 0.157
90 65.596 0.113 45 89.434 0.137
172 67.882 0.118
a
Bragg angles are listed for the location of the K1 component in the doublet, = 1.540593 Å.
Solution:
a) The solution is shown in Table 9.
Table 9. Indexing of the powder diffraction pattern of LaNi11.6Ge1.4.
I/I0 2q(o) FWHM(o) Q Q/Q1 h2+k2+l2 hkl a(Å)
33 15.561 0.165 0.03089 1.00 4 002 11.3799
31 22.099 0.128 0.06191 2.00 8 022 11.3678
87 27.131 0.122 0.09272 3.00 12 222 11.3763
80 31.423 0.116 0.12358 4.00 16 004 11.3784
487 35.255 0.104 0.15455 5.00 20 024 11.3757
847 38.745 0.100 0.18544 6.00 24 224 11.3765
1000 47.232 0.114 0.27047 8.76 35 135 11.3756
191 47.945 0.114 0.27821 9.01 36 244,006 11.3753
228 50.716 0.105 0.30912 10.01 40 026 11.3754
86 55.950 0.116 0.37084 12.01 48 444 11.3769
172 58.455 0.117 0.40181 13.01 52 046 11.3761
194 60.890 0.118 0.43272 14.01 56 246 11.3761
90 65.596 0.113 0.49450 16.01 64 008 11.3764
172 67.882 0.118 0.52539 17.01 68 028,446 11.3767
47 70.133 0.119 0.55629 18.01 72 066,228 11.3766
25 71.796 0.130 0.57941 18.76 75 157,555 11.3772
11 72.343 0.118 0.58707 19.01 76 266 11.3779
23 74.542 0.119 0.61807 20.01 80 048 11.3770
127 76.172 0.132 0.64126 20.76 83 357,119 11.3768
4 76.691 0.132 0.64868 21.00 84 248 11.3795
3 78.887 0.132 0.68024 22.02 88 466 11.3739
97 80.467 0.128 0.70311 22.76 91 139 11.3765
147 83.114 0.141 0.74163 24.01 96 448 11.3773
Copyright © 2009 by Springer 82
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
I/I0 2q(o) FWHM(o) Q Q/Q1 h2+k2+l2 hkl a(Å)
32 85.233 0.138 0.77263 25.01 100 0010,068 11.3766
158 87.336 0.151 0.80350 26.01 104 0210,268 11.3769
65 88.909 0.157 0.82662 26.76 107 159,377 11.3773
45 89.434 0.137 0.83434 27.01 108 2210,666 11.3773
Average= 11.3764
b) Analysis of the systematic absences is given below.
hkl 0kl hhl 00l
h+k,k+l,h+l k,l h,l l
Possible space groups: F̀3c or Fmc
Note: in the zone hhl nearly all non-overlapping reflections with h=2n+1, l=2n+1, i.e. 111,113,
115, 331, 333, etc. are absent. Only 555, 119 and 377 could be in principle present but they are
completely overlapped with other Bragg peaks. Thus, it is reasonable to conlcude that all hhl have
h = 2n, and l = 2n.
c) The solution is shown in Table 10.
The indexing result is highly probable given the excellent figures of merit, a face centered
lattice, and the apparent presence of glide plane c in space groups F̀3c and Fmc (see part b of
this solution).
Table 10. Figures of merit in the indexed powder diffraction pattern of LaNi11.6Ge1.4.
I/I0 2qobs Qobs hkl a 2qcalc |2qobs - 2qcalc| Qcalc | Qobs - Qcalc|
33 15.561 0.03089 002 11.3799 15.566 0.005 0.03091 0.00002
31 22.099 0.06191 022 11.3678 22.082 0.017 0.06181 0.00009
87 27.131 0.09272 222 11.3763 27.131 0.000 0.09272 0.00000
80 31.423 0.12358 004 11.3784 31.429 0.006 0.12363 0.00005
487 35.255 0.15455 024 11.3757 35.253 0.002 0.15453 0.00002
847 38.745 0.18544 224 11.3765 38.745 0.000 0.18544 0.00000
1000 47.232 0.27047 135 11.3756 47.229 0.003 0.27044 0.00003
191 47.945 0.27821 244,006 11.3753 47.940 0.005 0.27816 0.00005
228 50.716 0.30912 026 11.3754 50.712 0.004 0.30907 0.00005
86 55.950 0.37084 444 11.3769 55.953 0.003 0.37088 0.00004
172 58.455 0.40181 046 11.3761 58.453 0.002 0.40178 0.00003
194 60.890 0.43272 246 11.3761 60.888 0.002 0.43269 0.00003
90 65.596 0.49450 008 11.3764 65.596 0.000 0.49450 0.00000
172 67.882 0.52539 028,446 11.3767 67.884 0.002 0.52542 0.00003
47 70.133 0.55629 066,228 11.3766 70.135 0.002 0.55632 0.00003
25 71.796 0.57941 157,555 11.3772 71.802 0.006 0.57950 0.00008
11 72.343 0.58707 266 11.3779 72.354 0.011 0.58722 0.00015
23 74.542 0.61807 048 11.3770 74.547 0.005 0.61814 0.00007
127 76.172 0.64126 357,119 11.3768 76.176 0.004 0.64132 0.00006
4 76.691 0.64868 248 11.3795 76.716 0.025 0.64904 0.00036
3 78.887 0.68024 466 11.3739 78.866 0.021 0.67994
97 80.467 0.70311 139 11.3765 80.469 0.002 0.70313
Copyright © 2009 by Springer 83
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
I/I0 2qobs Qobs hkl a 2qcalc |2qobs - 2qcalc| Qcalc | Qobs - Qcalc|
147 83.114 0.74163 448 11.3773 83.123 0.009 0.74176
32 85.233 0.77263 0010,068 11.3766 85.235 0.002 0.77266
158 87.336 0.80350 0210,268 11.3769 87.341 0.005 0.80357
65 88.909 0.82662 159,377 11.3773 88.918 0.009 0.82675
45 89.434 0.83434 2210,666 11.3773 89.444 0.010 0.83449
Average= 11.3764 F27= 150(0.006,30) M20= 240
Average 0.0060 Average 0.00006
d) The solution is shown in Table 11.
Table 11. Least squares refinement of the lattice parameter of LaNi11.6Ge1.4.
I/I0 2q(o) Qobs h2+k2+l2 hkl a(Å) ATiAi ATibi
33 15.561 0.03089 4 002 11.3799 16 0.123550
31 22.099 0.06191 8 022 11.3678 64 0.495249
87 27.131 0.09272 12 222 11.3763 144 1.112658
80 31.423 0.12358 16 004 11.3784 256 1.977339
487 35.255 0.15455 20 024 11.3757 400 3.091039
847 38.745 0.18544 24 224 11.3765 576 4.450496
1000 47.232 0.27047 35 135 11.3756 1225 9.466400
191 47.945 0.27821 36 244, 006 11.3753 1296 10.015586
228 50.716 0.30912 40 026 11.3754 1600 12.364749
86 55.950 0.37084 48 444 11.3769 2304 17.800447
172 58.455 0.40181 52 046 11.3761 2704 20.894064
194 60.890 0.43272 56 246 11.3761 3136 24.232207
90 65.596 0.49450 64 008 11.3764 4096 31.648126
172 67.882 0.52539 68 028,446 11.3767 4624 35.726374
47 70.133 0.55629 72 066,228 11.3766 5184 40.053208
25 71.796 0.57941 75 157,555 11.3772 5625 43.456084
11 72.343 0.58707 76 266 11.3779 5776 44.617210
23 74.542 0.61807 80 048 11.3770 6400 49.445348
127 76.172 0.64126 83 357,119 11.3768 6889 53.224601
4 76.691 0.64868 84 248 11.3795 7056 54.489141
3 78.887 0.68024 88 466 11.3739 7744 59.861537
97 80.467 0.70311 91 139 11.3765 8281 63.982585
147 83.114 0.74163 96 448 11.3773 9216 71.196775
32 85.233 0.77263 100 0010,068 11.3766 10000 77.263497
158 87.336 0.80350 104 0210,268 11.3769 10816 83.563749
65 88.909 0.82662 107 159,377 11.3773 11449 88.448228
45 89.434 0.83434 108 2210,666 11.3773 11664 90.108658
Average= 11.3764 S= 128541 993.108902
According to the least squares method:
a* = (ATA)-1(ATb) = 993.1089/128541=0.00772609 Å-2
a = 11.3768 Å
Copyright © 2009 by Springer 84
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. Consider the X-ray powder diffraction pattern of CeRhGe3 shown in Figure 44 and found in
the file Ch14Pr02_MoKa.xy online. A total of 55 individual Bragg peaks are measurable up
to 2 = 46.5° and these are listed in Table 12 and also found in the file
Ch14Pr02_MoKa.pks online. Peak positions, intensities, and full widths at half maximum
have been determined using a profile fitting procedure. The observed Bragg angles are listed
for the K1 component in the doublet, = 0.709317 Å.
a) Using TREOR, ITO and DICVOL perform indexing of the powder diffraction pattern.
Make sure that you obtain a solution in each of the three programs.
b) Analyze the combinations of Miller indices of the observed Bragg reflections and
determine possible space groups describing symmetry of the material.
c) Perform least squares refinement of the unit cell dimensions using all available data
without refining any kind of a systematic error.1 Analyze the differences between the
observed and calculated 2 and decide whether the refinement of a zero shift or sample
displacement error is warranted. If it is, refine lattice parameters together with a zero shift
or sample displacement error.
CeRhGe3, Mo K
60
50
Intensity, Y (10 counts)
40
3
30
20
10
10 20 30 40
Bragg angle, 2 (deg.)
Figure 44. The X-ray powder diffraction pattern of CeRhGe3 collected on a Rigaku TTRAX rotating anode
powder diffractometer using Mo K radiation. Numerical data are available in the file
Ch14Pr02_MoKa.xy online.
1
If you do not have a preferred least squares refinement software you may download multiple programs
through IUCr or CCP14 Web sites at http://www.iucr.org or http://www.ccp14.ac.uk, respectively. One of
the simplest to use program, which also enables one to refine a zero shift parameter, is the UNITCELL.
Copyright © 2009 by Springer 85
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Table 12. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the CeRhGe3 powder diffraction pattern collected using Mo K radiation in the
range 7.5 2 46.5° (see Figure 44). Numerical data are found in the file Ch14Pr02_MoKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
5 8.100 0.091 9 35.507 0.071
110 10.091 0.073 49 35.654 0.071
270 13.086 0.068 112 36.055 0.070
789 15.303 0.070 10 36.288 0.078
1000 15.413 0.064 92 37.633 0.067
115 16.245 0.065 81 37.997 0.073
774 18.555 0.069 63 38.316 0.070
4 20.283 0.065 129 38.737 0.074
269 20.928 0.065 4 39.060 0.061
32 21.172 0.065 64 39.776 0.070
227 22.399 0.064 10 40.005 0.061
418 24.143 0.065 14 40.483 0.071
13 24.483 0.085 81 40.848 0.078
157 24.766 0.073 41 40.888 0.071
303 26.362 0.066 23 41.236 0.072
206 27.866 0.071 1 41.379 0.074
5 28.296 0.058 113 42.270 0.074
200 29.249 0.067 47 42.599 0.082
60 29.547 0.075 77 42.893 0.075
54 30.167 0.075 20 43.446 0.076
87 30.625 0.069 22 43.606 0.081
301 30.682 0.074 43 44.232 0.074
18 30.905 0.070 6 44.758 0.072
76 31.129 0.068 20 44.883 0.073
24 32.844 0.070 5 45.413 0.080
120 33.905 0.068 31 45.573 0.078
9 34.057 0.090 4 45.721 0.087
66 34.872 0.072
a
Bragg angles are listed for the location of the K1 component in the doublet, = 0.709317 Å.
Solution:
a) Indexing
Each indexing program should result in a solution in the tetragonal crystal system. The critical
portions of the outputs are shown below.
TREOR90 output
TOTAL NUMBER OF LINES = 55
A = 4.398650 .000105 A ALFA = 90.000000 .000000 DEG
B = 4.398650 .000105 A BETA = 90.000000 .000000 DEG
C = 10.034750 .000300 A GAMMA = 90.000000 .000000 DEG
UNIT CELL VOLUME = 194.15 A**3
H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS
0 0 2 .004995 .004997 -.000001 8.106 8.107 5.0180
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
1 0 1 .007750 .007750 .000000 10.101 10.101 4.0287
1 1 0 .013001 .013002 -.000001 13.094 13.095 3.1105
1 0 3 .017747 .017743 .000004 15.311 15.310 2.6622
1 1 2 .017999 .017999 .000001 15.420 15.420 2.6435
0 0 4 .019981 .019986 -.000005 16.253 16.255 2.5090
2 0 0 .026008 .026004 .000004 18.561 18.560 2.1992
2 0 2 .031004 .031001 .000003 20.283 20.282 2.0142
1 1 4 .032985 .032988 -.000003 20.928 20.929 1.9528
2 1 1 .033750 .033754 -.000004 21.172 21.173 1.9305
1 0 5 .037724 .037729 -.000006 22.399 22.401 1.8260
2 1 3 .043736 .043747 -.000011 24.143 24.146 1.6959
0 0 6 .044958 .044969 -.000011 24.483 24.486 1.6727
2 0 4 .045987 .045990 -.000003 24.766 24.767 1.6538
2 2 0 .051997 .052008 -.000011 26.362 26.365 1.5553
1 1 6 .057978 .057971 .000008 27.866 27.864 1.4729
3 0 1 .059745 .059758 -.000014 28.296 28.299 1.4510
3 0 2 .063506 29.192
2 1 5 .063748 .063733 .000014 29.249 29.246 1.4047
3 1 0 .065024 .065010 .000014 29.547 29.544 1.3908
1 0 7 .067718 .067708 .000009 30.167 30.165 1.3629
3 0 3 .069740 .069751 -.000011 30.625 30.628 1.3430
3 1 2 .069994 .070007 -.000013 30.682 30.685 1.3405
2 0 6 .070990 .070973 .000017 30.905 30.901 1.3311
2 2 4 .071997 .071994 .000003 31.129 31.128 1.3218
0 0 8 .079925 .079944 -.000019 32.844 32.848 1.2545
3 1 4 .085018 .084996 .000022 33.905 33.901 1.2163
3 2 1 .085760 .085762 -.000003 34.057 34.058 1.2111
3 2 2 .089510 34.817
3 0 5 .089784 .089737 .000047 34.872 34.863 1.1836
1 1 8 .092978 .092946 .000031 35.507 35.501 1.1631
2 1 7 .093724 .093712 .000012 35.654 35.652 1.1585
3 2 3 .095774 .095756 .000018 36.055 36.051 1.1460
2 2 6 .096974 .096977 -.000003 36.288 36.289 1.1389
4 0 0 .104031 .104016 .000015 37.633 37.630 1.0996
2 0 8 .105979 .105948 .000030 37.997 37.991 1.0894
1 0 9 .107698 .107681 .000018 38.316 38.313 1.0807
3 1 6 .109987 .109979 .000008 38.737 38.736 1.0694
4 1 1 .111757 .111767 -.000010 39.060 39.062 1.0609
4 1 2 .115514 39.738
3 2 5 .115724 .115742 -.000017 39.776 39.779 1.0426
3 3 0 .117006 .117018 -.000013 40.005 40.007 1.0368
3 0 7 .119701 .119717 -.000016 40.483 40.486 1.0251
4 1 3 .121776 .121760 .000017 40.848 40.845 1.0163
3 3 2 .122005 .122015 -.000010 40.888 40.890 1.0154
4 0 4 .124000 .124002 -.000003 41.236 41.237 1.0072
0 0 10 .124823 .124913 -.000090 41.379 41.395 1.0038
4 2 0 .130008 .130021 -.000012 42.270 42.272 .9836
2 2 8 .131946 .131953 -.000007 42.599 42.600 .9764
2 1 9 .133687 .133685 .000002 42.893 42.893 .9700
3 3 4 .136989 .137005 -.000016 43.446 43.449 .9582
1 1 10 .137950 .137915 .000035 43.606 43.600 .9549
4 1 5 .141739 .141746 -.000006 44.232 44.233 .9420
3 1 8 .144956 .144955 .000002 44.758 44.758 .9315
3 2 7 .145725 .145721 .000005 44.883 44.882 .9291
4 0 6 .149004 .148985 .000019 45.413 45.410 .9188
4 2 4 .150000 .150007 -.000007 45.573 45.574 .9157
2 0 10 .150924 .150917 .000006 45.721 45.720 .9129
0 0 11 .151145 45.756
NUMBER OF OBS. LINES = 55
NUMBER OF CALC. LINES = 59
M( 20)= 122 AV.EPS.= .0000064
F 20 = 256.( .001822, 43)
M( 30)= 74 AV.EPS.= .0000102
F 30 = 198.( .002449, 62)
M( 55)= 54 AV.EPS.= .0000126
F 55 = 192.( .002560, 112)
M CF. J.APPL.CRYST. 1(1968)108
F CF. J.APPL.CRYST. 12(1979)60
0 LINES ARE UNINDEXED
M-TEST= 122 UNINDEXED IN THE TEST= 0
Copyright © 2009 by Springer 87
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
ITO13 output
TETRAGONAL INDEXING
RECIPROCAL CONSTANTS (QX,QZ) ARE 517.30 99.39
THE DIRECT CONSTANTS ARE A= 4.3967 C= 10.0308
VOLUME = 193.9 ZEROSHIFT= -0.0124
DICVOL91 output
T E T R A G O N A L S Y S T E M
DIRECT PARAMETERS : A= 4.39877 C= 10.03453 VOLUME= 194.16
STANDARD DEVIATIONS : 0.00017 0.00048
H K L DOBS DCAL DOBS-DCAL QOBS QCAL 2TH.OBS 2TH.CAL DIF.2TH.
0 0 2 5.02157 5.01727 0.00431 0.039660.03973 8.100 8.107 -0.007
1 0 1 4.03265 4.02868 0.00396 0.061490.06161 10.091 10.101 -0.010
1 1 0 3.11244 3.11040 0.00204 0.103230.10336 13.086 13.095 -0.009
1 0 3 2.66366 2.66252 0.00114 0.140940.14106 15.303 15.310 -0.007
1 1 2 2.64476 2.64361 0.00115 0.142960.14309 15.413 15.420 -0.007
0 0 4 2.51015 2.50863 0.00151 0.158710.15890 16.245 16.255 -0.010
2 0 0 2.19989 2.19938 0.00051 0.206630.20673 18.555 18.559 -0.004
2 0 2 2.01419 2.01434 -0.00015 0.246490.24645 20.283 20.281 0.002
1 1 4 1.95278 1.95268 0.00010 0.262240.26226 20.928 20.929 -0.001
2 1 1 1.93052 1.93044 0.00008 0.268320.26834 21.172 21.173 -0.001
1 0 5 1.82601 1.82585 0.00016 0.299910.29996 22.399 22.401 -0.002
2 1 3 1.69586 1.69567 0.00019 0.347710.34779 24.143 24.146 -0.003
0 0 6 1.67266 1.67242 0.00024 0.357420.35753 24.483 24.487 -0.004
2 0 4 1.65384 1.65379 0.00005 0.365610.36563 24.766 24.767 -0.001
2 2 0 1.55533 1.55520 0.00013 0.413390.41346 26.362 26.364 -0.002
1 1 6 1.47291 1.47299 -0.00008 0.460940.46089 27.866 27.864 0.002
3 0 1 1.45098 1.45085 0.00013 0.474980.47507 28.296 28.299 -0.003
2 1 5 1.40468 1.40484 -0.00016 0.506810.50669 29.249 29.246 0.003
3 1 0 1.39083 1.39101 -0.00019 0.516960.51682 29.547 29.543 0.004
1 0 7 1.36288 1.36296 -0.00007 0.538370.53832 30.167 30.165 0.002
3 0 3 1.34298 1.34289 0.00008 0.554450.55452 30.625 30.627 -0.002
3 1 2 1.34054 1.34045 0.00009 0.556470.55654 30.682 30.684 -0.002
2 0 6 1.33110 1.33126 -0.00016 0.564390.56425 30.905 30.901 0.004
2 2 4 1.32176 1.32180 -0.00004 0.572390.57236 31.129 31.128 0.001
0 0 8 1.25450 1.25432 0.00018 0.635420.63560 32.844 32.849 -0.005
3 1 4 1.21634 1.21651 -0.00017 0.675910.67572 33.905 33.900 0.005
3 2 1 1.21107 1.21108 -0.00001 0.681810.68180 34.057 34.057 0.000
3 0 5 1.18361 1.18393 -0.00032 0.713810.71342 34.872 34.862 0.010
1 1 8 1.16311 1.16329 -0.00018 0.739190.73897 35.507 35.501 0.006
2 1 7 1.15847 1.15854 -0.00007 0.745130.74504 35.654 35.652 0.002
3 2 3 1.14601 1.14614 -0.00013 0.761420.76125 36.055 36.051 0.004
2 2 6 1.13889 1.13888 0.00001 0.770960.77098 36.288 36.288 0.000
4 0 0 1.09959 1.09969 -0.00011 0.827070.82691 37.633 37.629 0.004
2 0 8 1.08944 1.08958 -0.00014 0.842550.84233 37.997 37.992 0.005
1 0 9 1.08070 1.08077 -0.00007 0.856230.85612 38.316 38.313 0.003
3 1 6 1.06940 1.06945 -0.00005 0.874420.87435 38.737 38.735 0.002
4 1 1 1.06090 1.06088 0.00002 0.888490.88852 39.060 39.061 -0.001
3 2 5 1.04255 1.04249 0.00006 0.920030.92015 39.776 39.779 -0.003
4 1 2 1.04353 -0.00097 0.91832 39.737 0.039
3 3 0 1.03683 1.03680 0.00003 0.930220.93027 40.005 40.006 -0.001
3 0 7 1.02509 1.02502 0.00007 0.951650.95177 40.483 40.486 -0.003
* NUMBER OF LINES
.- INPUT DATA = 40
.- CALCULATED = 85
* MEAN ABSOLUTE DISCREPANCIES
<Q> =0.1049E-03
<DELTA(2-THETA)> =0.3571E-02
MAX. ERROR ACCEPTED (DEG. 2-THETA) =0.4500E-01
* FIGURES OF MERIT
1.- M( 40) = 53.3 (REF. 4)
2.- F( 40) = 131.8(0.0036, 85) (REF. 5)
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
b) Possible space groups
The analysis of Miller indices points to a body-centered lattice without additional systematic
absences. Thus possible space groups symmetry include
I4/mmm, Ìm2, Ì2m, I4mm, I422, I4/m, Ì4, and I
c) Refinement of lattice parameters
The least squares refinement of lattice parameters (UNITCELL) results in
a= 4.3987(1), c = 10.0348(4) Å
The plot of differences between the observed and calculated 2 is shown below and it indicates
the presence of a small systematic error. Note that one point (encircled in red) falls off from the
2 vs. 2 plot (weak Bragg peak, whose position is difficult to determine accurately), and it may
be excluded from the refinement.
The least squares refinement of lattice parameters together with the zero shift error by using the
UNITCELL program results in
a= 4.3979(1), c = 10.0329(3) Å, 20 = 0.0069.
0.015
0.01
0.005
2 (obs)-2 (calc)
0
0 5 10 15 20 25 30 35 40 45 50
-0.005
-0.01
-0.015
-0.02
Bragg angle, 2 (deg)
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
3. Consider the X-ray powder diffraction pattern of SrSi2 shown in Figure 45 and found in the
file Ch14Pr03_MoKa.xy online. A total of 20 individual Bragg peaks are measurable up to
2 = 33°. They are listed in Table 13 and also found in the file Ch14Pr03_MoKa.pks online.
Peak positions, intensities, and full widths at half maximum have been determined using a
profile fitting procedure. The observed Bragg angles are listed for the K1 component in the
doublet, = 0.709317 Å.
a) Conduct ab initio indexing of the powder diffraction pattern manually, i.e. using a
spreadsheet rather than any kind of crystallographic software. Compute the FN and M20
figures of merit and discuss both the probability of the determined unit cell and the
accuracy of the observed Bragg angles.
b) Now, perform the indexing of the same pattern using TREOR, ITO and DICVOL. Make
sure that you obtain a solution in each of the three programs.
c) Analyze the combinations of Miller indices of the observed reflections and determine
possible space groups, which characterize the symmetry of the material.
16
SrSi2, Mo K
14
12
Intensity, Y (10 counts)
10
3
0
10 15 20 25 30
Bragg angle, 2 (deg.)
Figure 45. The X-ray powder diffraction pattern of SrSi2 collected on a Rigaku TTRAX rotating anode
powder diffractometer using Mo K radiation. Numerical data are available in the file
Ch14Pr03_MoKa.xy online.
Copyright © 2009 by Springer 90
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Table 13. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the powder diffraction pattern of SrSi2 collected using Mo K radiation in the
range 8 2 33° (see Figure 45). Numerical data are found in the file Ch14Pr03_MoKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
80 8.872 0.091 396 23.484 0.079
38 10.851 0.080 101 25.128 0.084
1000 13.999 0.080 57 25.912 0.080
626 15.337 0.081 72 26.672 0.080
20 17.713 0.081 114 27.418 0.076
64 18.794 0.080 200 28.848 0.081
29 19.815 0.079 34 29.540 0.079
203 20.791 0.081 12 31.533 0.081
54 21.724 0.076 104 32.170 0.077
a
Bragg angles are listed for the location of the K1 component in the doublet, = 0.709317 Å.
Solution:
a) Manual ab initio indexing and figures of merit
Low Bragg angle peaks appear to be regularly spaced. Thus, cubic crystal system is highly
feasible and the result of manual indexing is shown in Table 14.
Table 14. Manual indexing of the powder diffraction pattern of SrSi2 using 20 low Bragg angle peaks and
assuming cubic symmetry.
I/I0 2 FWHM 1/d2 Q/Q1 h2+k2+l2 hkl a(Å)
80 8.872 0.091 0.047561 1.00 2 011 6.485
38 10.851 0.080 0.071074 1.49 3 111 6.497
1000 13.999 0.080 0.118061 2.48 5 012 6.508
626 15.337 0.081 0.141566 2.98 6 112 6.510
20 17.713 0.081 0.188449 3.96 8 022 6.515
64 18.794 0.080 0.211940 4.46 9 122, 003 6.517
29 19.815 0.079 0.235357 4.95 10 013 6.518
203 20.791 0.081 0.258852 5.44 11 113 6.519
54 21.724 0.076 0.282321 5.94 12 222 6.520
70 22.621 0.084 0.305807 6.43 13 023 6.520
396 23.484 0.079 0.329252 6.92 14 123 6.521
101 25.128 0.084 0.376198 7.91 16 004 6.522
57 25.912 0.080 0.399631 8.40 17 014, 223 6.522
72 26.672 0.080 0.422987 8.89 18 114, 033 6.523
114 27.418 0.076 0.446519 9.39 19 133 6.523
200 28.848 0.081 0.493298 10.37 21 124 6.525
34 29.540 0.079 0.516716 10.86 22 233 6.525
12 31.533 0.081 0.586966 12.34 25 034, 005 6.526
104 32.170 0.077 0.610288 12.83 26 134, 015 6.527
43 32.797 0.076 0.633650 13.32 27 115, 333 6.528
The first numbers in the column labeled Q/Q1 have decimal fractions close to 0 and 0.5. As Bragg
angle increases, the deviations from 0 and 0.5 systematically increase, which is a good indication
of a systematic error in Bragg angles (zero shift or sample displacement). Thus, the integers in
the column labeled h2+k2+l2 are obtained by multiplying the contents of column Q/Q1 by 2 and
rounding. The corresponding indices and calculated unit cell dimensions are listed in columns
labeled hkl and a, respectively.
Copyright © 2009 by Springer 91
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Zero-shift can be manually adjusted to get a better agreement of Q values (it can be easily found
using any spreadsheet program). Zero-shift 2 = 0.075º applied as 2corr. = 2meas. - 2
improves the Q/Q1 values as shown in Table 15 and yields an average unit cell dimension a =
6.5417(8) Å.
Table 15. Manual indexing of the powder diffraction pattern of SrSi2 after correcting the data for the zero
shift = 0.075o.
I/I0 2corr FWHM 1/d2 Q/Q1 h2+k2+l2 hkl a(Å)
80 8.797 0.091 0.04676 1.00 2 011 6.5399
38 10.776 0.080 0.07010 1.50 3 111 6.5419
1000 13.924 0.080 0.11681 2.50 5 012 6.5426
626 15.262 0.081 0.14019 3.00 6 112 6.5420
20 17.638 0.081 0.18687 4.00 8 022 6.5430
64 18.719 0.080 0.21027 4.50 9 122, 003 6.5424
29 19.740 0.079 0.23360 5.00 10 013 6.5428
203 20.716 0.081 0.25701 5.50 11 113 6.5422
54 21.649 0.076 0.28040 6.00 12 222 6.5419
70 22.546 0.084 0.30381 6.50 13 023 6.5414
396 23.409 0.079 0.32718 7.00 14 123 6.5414
101 25.053 0.084 0.37399 8.00 16 004 6.5408
57 25.837 0.080 0.39736 8.50 17 014, 223 6.5408
72 26.597 0.080 0.42066 9.00 18 114, 033 6.5414
114 27.343 0.076 0.44413 9.50 19 133 6.5407
200 28.773 0.081 0.49079 10.50 21 124 6.5412
34 29.465 0.079 0.51416 11.00 22 233 6.5413
12 31.458 0.081 0.58425 12.49 25 034, 005 6.5414
104 32.095 0.077 0.60752 12.99 26 134, 015 6.5419
43 32.722 0.076 0.63084 13.49 27 115, 333 6.5422
At this point we only know that the lattice is primitive. Thus, the number of possible Bragg
reflections, which is required to compute the figures of merit is Nposs = 27 – 3 (the h2+k2+l2 sums
cannot be 7, 15, and 23, all other are assumed to be allowed). The F20 and M20 figures of merit are
computed in Table 16. Considering the values of both figures of merit, the found unit cell is
highly probable. Furthermore, since additional systematic absences introduced by a space group
symmetry decrease the Nposs, both figures of merit will only increase, if any.
Table 16. Figures of merit in the indexed pattern of SrSi2 after zero shift correction assuming a primitive
Bravais lattice without additional systematic absences, which may be introduced by glide planes and screw
axes.
I/I0 2corr Qobs hkl a 2calc |2obs - 2calc| Qcalc | Qobs - Qcalc|
80 8.797 0.04676 011 6.5399 8.795 0.002 0.04674 0.00002
38 10.776 0.07010 111 6.5419 10.776 0.000 0.07010 0.00000
1000 13.924 0.11681 012 6.5426 13.926 0.002 0.11684 0.00003
626 15.262 0.14019 112 6.5420 15.263 0.001 0.14021 0.00002
20 17.638 0.18687 022 6.5430 17.641 0.003 0.18694 0.00007
64 18.719 0.21027 122, 003 6.5424 18.721 0.002 0.21031 0.00004
29 19.740 0.23360 013 6.5428 19.743 0.003 0.23368 0.00008
203 20.716 0.25701 113 6.5422 20.717 0.001 0.25705 0.00004
54 21.649 0.28040 222 6.5419 21.650 0.001 0.28041 0.00001
70 22.546 0.30381 023 6.5414 22.545 0.001 0.30378 0.00003
396 23.409 0.32718 123 6.5414 23.408 0.001 0.32715 0.00003
101 25.053 0.37399 004 6.5408 25.049 0.004 0.37389 0.00010
57 25.837 0.39736 014, 223 6.5408 25.833 0.004 0.39725 0.00011
Copyright © 2009 by Springer 92
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
I/I0 2corr Qobs hkl a 2calc |2obs - 2calc| Qcalc | Qobs - Qcalc|
72 26.597 0.42066 114, 033 6.5414 26.596 0.001 0.42062 0.00004
114 27.343 0.44413 133 6.5407 27.339 0.004 0.44399 0.00014
200 28.773 0.49079 124 6.5412 28.771 0.002 0.49072 0.00007
34 29.465 0.51416 233 6.5413 29.463 0.002 0.51409 0.00007
12 31.458 0.58425 034, 005 6.5414 31.457 0.001 0.58420 0.00005
104 32.095 0.60752 134, 015 6.5419 32.096 0.001 0.60756 0.00004
43 32.722 0.63084 115, 333 6.5419 32.725 0.003 0.63093 0.00009
Average= 6.5417 F20= 412(0.002,24) M20= 242
Average 0.002 Average 0.00005
Considering the differences between the observed and calculated Bragg angles after the zero shift
correction, the accuracy of Bragg angle is excellent.
b) automatic indexing using TREOR, ITO and DICVOL
Using uncorrected Bragg angles (Table 4), the following solution was found by TREOR90
A = 4.613177 .001542 A ALFA = 90.000000 .000000 DEG
B = 4.613177 .001542 A BETA = 90.000000 .000000 DEG
C = 6.515528 .005734 A GAMMA = 90.000000 .000000 DEG
UNIT CELL VOLUME = 138.66 A**3
…
NUMBER OF OBS. LINES = 20
NUMBER OF CALC. LINES = 31
M( 20)= 26 AV.EPS.= .0000420
F 20 = 38.( .014776, 36)
Although the tetragonal unit cell is related to the correct cubic unit cell, the figures of
merit are quite low. The failure to find a cubic unit cell is related to a relatively large
systematic error present in the data.
Next, the array of corrected data (Table 5), results in the following solution, which is the
same as that found manually.
A = 6.541549 .000125 A ALFA = 90.000000 .000000 DEG
B = 6.541549 .000125 A BETA = 90.000000 .000000 DEG
C = 6.541549 .000125 A GAMMA = 90.000000 .000000 DEG
UNIT CELL VOLUME = 279.93 A**3
…
NUMBER OF OBS. LINES = 20
NUMBER OF CALC. LINES = 20
M( 20)= 267 AV.EPS.= .0000064
F 20 = 462.( .001883, 23)
ITO13 finds the correct solution employing uncorrected data:
CUBIC INDEXING
THE RECIPROCAL CONSTANT (QX) IS 233.71
THE DIRECT CONSTANT IS A= 6.5413
VOLUME = 279.9 ZEROSHIFT= 0.0738
DICVOL91 employed with all defaults and using uncorrected Bragg angles, finds no solution in
the cubic crystal system, but finds a tetragonal unit cell with a c 6.5 Å and an orthorhombic
unit cell, similar to the tetragonal unit cell found by TREOR90 when the uncorrected data were
Copyright © 2009 by Springer 93
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
employed. Yet again, the failure to find the relatively simple cubic unit cell is related to the
presence of a systematic error in the data.
When corrected Bragg angle data were employed (Table 5), the true solution is easily found:
C U B I C S Y S T E M
DIRECT PARAMETERS : A= 6.54152 VOLUME= 279.92
STANDARD DEVIATIONS : 0.00019
The examples of automatic indexing discussed above contain a useful take-home message: when
experimental data are affected by a systematic error, manual ab initio indexing can be
considerably more reliable when compared to an automatic indexing (see Table 4, where despite
systematic and considerable deviations from the whole we were able to recognize that the lattice
is indeed cubic).
c) Space group symmetry
Bravais lattice is primitive. There are no restrictions on reflections of types 0kl (011, 012, etc. are
present) and hhl (111, 112, etc are present). Among resolved 00l, only 004 is observed; 001 and
002 are extinct. Two other, 003 and 005, are present in the list but both are completely overlapped
with 122 and 034, respectively. Thus, it is reasonable to assume that for 00l only l = 4n are
allowed. After consulting with Table 2.17, these conditions correspond to one of the two possible
space groups:
P4132 or P4332.
The two groups are enantiomorphous and indistinguishable from powder diffraction. If our
reasoning is incorrect, and either or both 003 and 005 have non-zero intensities, then no
reflections are forbidden and we will need to test one or more from the following space groups:
P23, Pm, P432, P3m, or Pmm.
Copyright © 2009 by Springer 94
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
4. Consider the X-ray powder diffraction pattern of Li2Sn(OH)6 shown in Figure 46 and found
in the file Ch14Pr04_CuKa.xy online. A total of 38 individual Bragg peaks are measurable
up to 2 = 51° and these are listed in Table 17. The values in Table 17 have been corrected
for the sample displacement error. All 88 (uncorrected) peaks observed below 2 = 71 can
be found in the file Ch14Pr04_CuKa.pks online. Peak positions (listed for the K1
component in the doublet, = 1.540593 Å), intensities, and full widths at half maximum have
been determined using a profile fitting procedure.
a) Using data from Table 17 and TREOR, ITO and DICVOL, perform indexing of the
powder diffraction pattern. Try to obtain solution in each of the three programs.
b) Analyze the observed Miller indices and determine possible space groups of the material.
c) Perform the least squares refinement of the unit cell dimensions using all available data
(file Ch14Pr04_CuKa.pks online) without refining any kind of a systematic error and
then refine lattice parameters together with a zero shift or a sample displacement error.
70
Li2Sn(OH)6, Cu K
60
Intensity, Y (10 counts)
50
3
40
30
20
10
0
20 30 40 50 60 70
Bragg angle, 2 (deg.)
Figure 46. The X-ray powder diffraction pattern of Li2Sn(OH)6 collected on a Scintag XDS2000 powder
diffractometer using CuK radiation. Numerical data are available in the file Ch14Pr04_CuKa.xy online.
Table 17. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the powder diffraction pattern of Li2Sn(OH)6 collected using Cu K radiation in
the range 18 2 51° (see Figure 46). Numerical data are found in the file Ch14Pr04_CuKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
197 18.802 0.096 18 38.990 0.069
1000 19.041 0.108 47 39.070 0.069
288 19.213 0.107 193 39.428 0.069
150 20.740 0.090 29 39.503 0.069
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I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
337 23.916 0.083 96 41.137 0.075
1 25.361 0.083 1 41.721 0.075
344 29.541 0.054 19 42.211 0.075
334 32.114 0.074 3 42.565 0.075
18 33.143 0.074 1 43.545 0.075
103 33.478 0.074 7 42.508 0.075
12 34.576 0.074 158 44.405 0.063
1 34.980 0.074 79 46.520 0.076
28 35.689 0.074 33 46.825 0.076
55 36.275 0.074 36 48.045 0.076
16 37.620 0.069 106 48.948 0.076
105 38.141 0.069 3 49.132 0.076
63 38.375 0.069 64 49.489 0.076
83 38.589 0.069 23 49.981 0.076
9 38.845 0.069 26 50.517 0.076
a
Bragg angles are listed for the location of the CuK1 component in the doublet, = 1.540593 Å. Peak
positions are already corrected for the sample shift -0.15 mm assuming goniometer radius of 250 mm.
Solution:
a) Indexing
Each indexing program should result in the monoclinic solution. The critical outputs are shown
below. DICVOL does not produce any reasonable indexing solution until an impurity Bragg peak
observed at 42.501 2 (uncorrected) or 42.565 2 (corrected) is eliminated from the input data.
TREOR output
NUMBER OF SINGLE INDEXED LINES = 34
TOTAL NUMBER OF LINES = 38
A = 9.297244 0.001022 A ALFA = 90.000000 0.000000 DEG
B = 5.401130 0.000785 A BETA = 96.607780 0.010690 DEG
C = 5.160748 0.000671 A GAMMA = 90.000000 0.000000 DEG
UNIT CELL VOLUME = 257.43 A**3
H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM.
-1 0 1 0.026688 0.026649 0.000039 18.805 18.791 4.7151 1968
1 1 0 0.027295 0.027295 0.000000 19.019 19.019 4.6624 9999
2 0 0 0.027843 0.027825 0.000018 19.211 19.205 4.6163 2874
1 0 1 0.032416 0.032417 -0.000002 20.745 20.745 4.2783 1501
0 1 1 0.042907 0.042916 -0.000009 23.910 23.912 3.7186 3372
2 1 0 0.048186 0.048164 0.000022 25.361 25.355 3.5090 7
-2 1 1 0.064998 0.064973 0.000026 29.541 29.535 3.0213 3434
2 1 1 0.076504 0.076509 -0.000005 32.114 32.115 2.7849 3335
-3 0 1 0.076531 32.120
0 2 0 0.081346 0.081356 -0.000010 33.143 33.145 2.7007 184
3 1 0 0.082951 0.082946 0.000006 33.478 33.477 2.6745 1033
1 2 0 0.088313 0.088312 0.000001 34.576 34.576 2.5920 117
0 0 2 0.090324 0.090307 0.000017 34.980 34.977 2.5630 14
3 0 1 0.093902 0.093836 0.000066 35.689 35.676 2.5137 275
-3 1 1 0.096907 0.096870 0.000037 36.275 36.268 2.4744 552
0 2 1 0.103962 0.103932 0.000029 37.620 37.615 2.3890 156
-2 0 2 0.106753 0.106596 0.000158 38.141 38.112 2.3575 1046
-1 2 1 0.108018 0.108005 0.000013 38.375 38.373 2.3437 626
2 2 0 0.109180 0.109181 -0.000001 38.589 38.589 2.3312 832
0 1 2 0.110577 0.110646 -0.000069 38.845 38.858 2.3164 88
4 0 0 0.111372 0.111301 0.000071 38.990 38.977 2.3081 178
Copyright © 2009 by Springer 96
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
-1 1 2
0.111812 0.111834 -0.000022 39.070 39.074 2.3036 467
1 2 1
0.113788 0.113773 0.000015 39.428 39.425 2.2835 1930
3 1 1
0.114204 0.114175 0.000030 39.503 39.498 2.2793 285
1 1 2
0.123431 0.123370 0.000060 41.137 41.127 2.1925 963
-2 1 2
0.126803 0.126934 -0.000132 41.721 41.744 2.1631 4
2 0 2
0.129662 0.129669 -0.000006 42.211 42.212 2.1392 188
4 1 0
0.131408 0.131640 -0.000231 42.508 42.547 2.1249 67
0.131745 42.565 2.1222 25
2 2 1 0.137583 0.137526 0.000057 43.545 43.535 2.0767 2
-4 1 1 0.142794 0.142680 0.000114 44.405 44.386 2.0384 1584
-3 1 2 0.155949 0.155948 0.000002 46.520 46.520 1.9505 789
-3 2 1 0.157886 0.157887 -0.000001 46.825 46.825 1.9386 326
4 1 1 0.165727 0.165753 -0.000026 48.045 48.049 1.8921 357
0 2 2 0.171628 0.171663 -0.000034 48.948 48.953 1.8593 1060
-1 2 2 0.172841 0.172851 -0.000010 49.132 49.134 1.8528 26
3 2 1 0.175203 0.175191 0.000011 49.489 49.487 1.8403 640
-4 0 2 0.178479 0.178535 -0.000055 49.981 49.989 1.8233 231
-5 0 1 0.182075 0.182063 0.000012 50.517 50.515 1.8052 259
NUMBER OF OBS. LINES = 38
NUMBER OF CALC. LINES = 38
M( 20)= 60 AV.EPS.= 0.0000300
F 20 = 103.(0.006320, 31)
M( 38)= 42 AV.EPS.= 0.0000384
F 38 = 96.(0.007117, 56)
M CF. J.APPL.CRYST. 1(1968)108
F CF. J.APPL.CRYST. 12(1979)60
1 LINES ARE UNINDEXED
ITO15 output
SOLUTION NR. 1
117.23 342.57 380.33 0.00 48.41 0.00 20. 43.4
************************************************
* USE THE LIST TO FIND SYSTEMATIC ABSENCES *
************************************************
LIST OF ALL OBSERVED AND CALCULATED LINES UP TO THE 32ST.
IF THE TWOTHETAS DIFFER MORE THAN 0.049 DEGREES,
A BLANK LINE IS INSERTED.
TWOTHETA D H K L Q
9.572 9.233 1 0 0 117.3
16.398 5.401 0 1 0 342.8
17.283 5.127 0 0 1 380.5
18.791 4.719 1 0 -1 449.1
18.797 4.717 *OBSERVED 449.4 43
19.019 4.663 1 1 0 460.0
19.036 4.658 *OBSERVED 460.8 99
19.206 4.618 2 0 0 469.0
19.208 4.617 *OBSERVED 469.1 53
20.735 4.280 *OBSERVED 545.8 38
20.743 4.279 1 0 1 546.2
23.909 3.719 0 1 1 723.1
23.911 3.719 *OBSERVED 723.2 57
24.393 3.646 2 0 -1 752.2
25.036 3.554 1 1 -1 791.7
25.353 3.510 2 1 0 811.6
Copyright © 2009 by Springer 97
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
25.356 3.510 *OBSERVED 811.8 2
26.553 3.354 1 1 1 888.9
27.416 3.251 2 0 1 946.4
28.979 3.079 3 0 0 1055.0
29.532 3.022 2 1 -1 1094.8
29.536 3.022 *OBSERVED 1095.0 58
32.110 2.785 2 1 1 1289.0
32.109 2.785 *OBSERVED 1288.9 57
32.118 2.785 3 0 -1 1289.6
33.139 2.701 0 2 0 1370.6
33.138 2.701 *OBSERVED 1370.5 13
33.473 2.675 3 1 0 1397.6
33.473 2.675 *OBSERVED 1397.6 31
34.569 2.593 1 2 0 1487.8
34.571 2.592 *OBSERVED 1487.9 10
34.970 2.564 0 0 2 1521.4
34.975 2.563 *OBSERVED 1521.8 3
35.207 2.547 1 0 -2 1541.5
35.671 2.515 3 0 1 1581.0
35.684 2.514 *OBSERVED 1582.1 16
36.264 2.475 3 1 -1 1632.2
36.270 2.475 *OBSERVED 1632.7 23
37.437 2.400 1 0 2 1735.7
37.607 2.390 0 2 1 1750.9
37.615 2.389 *OBSERVED 1751.6 12
38.106 2.360 2 0 -2 1796.0
38.136 2.358 *OBSERVED 1798.6 32
38.365 2.344 1 2 -1 1819.5
38.370 2.344 *OBSERVED 1819.9 24
38.582 2.332 2 2 0 1839.4
38.584 2.332 *OBSERVED 1839.5 28
38.840 2.317 *OBSERVED 1863.1 9
38.849 2.316 0 1 2 1864.0
38.973 2.309 4 0 0 1875.4
38.985 2.308 *OBSERVED 1876.5 13
39.067 2.304 1 1 -2 1884.1
39.065 2.304 *OBSERVED 1883.9 21
39.417 2.284 1 2 1 1916.6
39.423 2.284 *OBSERVED 1917.2 43
39.491 2.280 3 1 1 1923.5
39.498 2.280 *OBSERVED 1924.2 16
40.943 2.202 4 0 -1 2061.5
41.117 2.194 1 1 2 2078.3
41.132 2.193 *OBSERVED 2079.7 30
41.573 2.171 2 2 -1 2122.6
Copyright © 2009 by Springer 98
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
41.716 2.163 *OBSERVED 2136.5 2
41.736 2.162 2 1 -2 2138.5
42.202 2.140 2 0 2 2184.4
42.206 2.139 *OBSERVED 2184.7 13
42.503 2.125 *OBSERVED 2214.1 8
42.542 2.123 4 1 0 2218.0
42.560 2.122 *OBSERVED 2219.8 4
43.210 2.092 3 0 -2 2284.8
43.526 2.078 2 2 1 2316.8
43.540 2.077 *OBSERVED 2318.2 1
44.381 2.040 4 1 -1 2404.0
44.400 2.039 *OBSERVED 2406.0 39
44.588 2.031 3 2 0 2425.4
44.825 2.020 4 0 1 2449.9
45.563 1.989 2 1 2 2526.9
46.512 1.951 3 1 -2 2627.4
46.515 1.951 *OBSERVED 2627.7 27
46.817 1.939 3 2 -1 2660.0
46.820 1.939 *OBSERVED 2660.3 17
THERE ARE 0 UNINDEXED LINES AMONGST THE FIRST 20 INDEXED LINES.
SOLUTION NR. 1
117.18 342.54 380.23 0.00 48.55 0.00 20. 56.4
ZEROSHIFT= 0.0054 DEGREES TWOTHETA
********************************************************************
* THIS ZEROSHIFT COULD CORRESPOND TO A SPECIMEN DISPLACEMENT OF *
* 0.02 MILLIMETER IN A "STANDARD" DIFFRACTOMETER. *
* ONLY THE "OWNER" OF THE DATA CAN JUDGE ITS PROBABILITY. *
********************************************************************
****************************************************************************
* THE OBSERVED POSITIONS OF THE DIFFRACTION LINES ARE CORRECTED HERE *
* WITH A *ZERO-CORRECTION*, WHICH STANDS FOR THE SUM OF A REAL *
* ZEROPOINT ERROR PLUS A SPECIMEN DISPLACEMENT ERROR PLUS A TRANSPARENCY *
* ERROR. THE CORRECTION IS A CONSTANT OVER THE 2THETA RANGE. *
****************************************************************************
THE DIRECT CONSTANTS OF THESE LATTICES
A B C ALFA BETA GAMMA VOLUME
9.2995 5.4031 5.1626 90.0000 96.6032 90.0000 257.68
DICVOL91 output
SEARCH OF MONOCLINIC SOLUTION(S) WITHIN THE LIMITS ON LINEAR PARAMETERS
***********************************************************************
(SLIGHT TOLERANCE ACCEPTED): A MAX= 9.946 B MAX= 9.946 C MAX= 9.946
VOLUME DOMAIN BEING SCANNED :
===========================
LOWER BOUND = 10.00 A**3 HIGHER BOUND = 410.00 A**3
ANGLE RANGE SCANNED : BETA MIN= 90.000 Deg. BETA MAX= 95.000 Deg.
ANGLE RANGE SCANNED : BETA MIN= 95.000 Deg. BETA MAX=100.000 Deg.
M O N O C L I N I C S Y S T E M
Copyright © 2009 by Springer 99
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
DIRECT PARAMETERS : A= 9.2969 B= 5.4009 C= 5.1607 BETA= 96.607 VOLUME= 257.41
STANDARD DEVIATIONS : 0.0011 0.0008 0.0007 0.011
H K L DOBS DCAL DOBS-DCAL QOBS QCAL 2TH.OBS 2TH.CAL DIF.2TH.
1 0 -1 4.71572 4.71846 -0.00274 0.044970.04492 18.802 18.791 0.011
1 1 0 4.65706 4.66219 -0.00513 0.046110.04601 19.041 19.020 0.021
2 0 0 4.61576 4.61756 -0.00181 0.046940.04690 19.213 19.205 0.008
1 0 1 4.27924 4.27813 0.00110 0.054610.05464 20.740 20.745 -0.005
0 1 1 3.71766 3.71818 -0.00052 0.072350.07233 23.916 23.913 0.003
2 1 0 3.50902 3.50971 -0.00068 0.081210.08118 25.361 25.356 0.005
2 1 -1 3.02132 3.02183 -0.00050 0.109550.10951 29.541 29.536 0.005
2 1 1 2.78488 2.78472 0.00017 0.128940.12896 32.114 32.116 -0.002
3 0 -1 2.78429 0.00059 0.12899 32.121 -0.007
0 2 0 2.70073 2.70047 0.00026 0.137100.13713 33.143 33.146 -0.003
3 1 0 2.67447 2.67446 0.00001 0.139810.13981 33.478 33.478 0.000
1 2 0 2.59201 2.59193 0.00008 0.148840.14885 34.576 34.577 -0.001
0 0 2 2.56299 2.56320 -0.00021 0.152230.15221 34.980 34.977 0.003
3 0 1 2.51368 2.51450 -0.00082 0.158260.15816 35.689 35.677 0.012
3 1 -1 2.47441 2.47479 -0.00038 0.163330.16328 36.275 36.269 0.006
0 2 1 2.38898 2.38924 -0.00027 0.175220.17518 37.620 37.616 0.004
2 0 -2 2.35753 2.35923 -0.00169 0.179920.17966 38.141 38.113 0.028
1 2 -1 2.34369 2.34376 -0.00007 0.182050.18204 38.375 38.374 0.001
2 2 0 2.33119 2.33109 0.00009 0.184010.18403 38.589 38.591 -0.002
0 1 2 2.31641 2.31566 0.00076 0.186370.18649 38.845 38.858 -0.013
4 0 0 2.30813 2.30878 -0.00065 0.187710.18760 38.990 38.979 0.011
1 1 -2 2.30359 2.30332 0.00027 0.188450.18849 39.070 39.075 -0.005
1 2 1 2.28349 2.28358 -0.00009 0.191780.19176 39.428 39.426 0.002
3 1 1 2.27933 2.27956 -0.00023 0.192480.19244 39.503 39.499 0.004
1 1 2 2.19249 2.19299 -0.00050 0.208030.20793 41.137 41.127 0.010
2 1 -2 2.16314 2.16197 0.00117 0.213710.21395 41.721 41.745 -0.024
2 0 2 2.13915 2.13907 0.00009 0.218530.21855 42.211 42.213 -0.002
4 1 0 2.12489 2.12295 0.00195 0.221480.22188 42.508 42.549 -0.041
2 2 1 2.07666 2.07703 -0.00037 0.231880.23180 43.545 43.537 0.008
4 1 -1 2.03842 2.03916 -0.00074 0.240670.24049 44.405 44.388 0.017
3 1 -2 1.95055 1.95051 0.00004 0.262840.26285 46.520 46.521 -0.001
3 2 -1 1.93855 1.93848 0.00008 0.266100.26612 46.825 46.827 -0.002
4 1 1 1.89214 1.89193 0.00021 0.279320.27938 48.045 48.051 -0.006
0 2 2 1.85932 1.85909 0.00023 0.289260.28933 48.948 48.954 -0.006
1 2 -2 1.85279 1.85269 0.00010 0.291310.29134 49.132 49.135 -0.003
3 2 1 1.84025 1.84026 0.00000 0.295290.29529 49.489 49.489 0.000
4 0 -2 1.82329 1.82295 0.00034 0.300810.30092 49.981 49.991 -0.010
5 0 -1 1.80519 1.80518 0.00001 0.306870.30687 50.517 50.517 0.000
* NUMBER OF LINES
.- INPUT DATA = 37
.- CALCULATED = 56
* MEAN ABSOLUTE DISCREPANCIES
<Q> =0.6777E-04
<DELTA(2-THETA)> =0.7734E-02
MAX. ERROR ACCEPTED (DEG. 2-THETA) =0.4500E-01
* FIGURES OF MERIT
1.- M( 37) = 40.4 (REF. 4)
2.- F( 37) = 85.4(0.0077, 56) (REF. 5)
b) Possible space groups symmetry
The analysis of Miller indices points to a primitive unit cell with the following systematic
absences h0l, h+l=2n and 0k0, k=2n. Hence, only one space group symmetry is possible:
P21/n
Copyright © 2009 by Springer 100
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
c) Refinement of lattice parameters
The least squares refinement of lattice parameters employing WinCSD and using all reflections
without applying corrections for a systematic error results in
a = 9.3053(6), b = 5.4059(4), c = 5.1663(4) Å, = 96.602(6).
The plot of differences between the observed and calculated 2 is shown below (blue colored
squares). Clearly, the plot points to the presence of a systematic error in the data. Note that
several points (encircled in the figure) fall off from the 2 vs. 2 plot. Analysis of the powder
diffraction pattern indicates that all of them are weak and/or heavily overlapped Bragg peaks,
whose positions is difficult to determine accurately. These Bragg reflections, therefore, may be
excluded from the refinement.
0.05
0.04
0.03
0.02
0.01
-0.01
-0.02
-0.03
-0.04
-0.05
-0.06 noshft
shift
-0.07
10 20 30 40 50 60 70
The least squares refinement of lattice parameters together with the sample shift and excluding
marked reflections results in
a = 9.2978(4), b = 5.4022(3), c = 5.1621(3) Å, = 96.601(2)
The refined sample displacement is -0.126(7) mm for a goniometer radius 250 mm.
Copyright © 2009 by Springer 101
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5. Consider the X-ray powder diffraction pattern of tea2Mo6O19 (tea is tetraethyl-ammonium,
[N(C2H5)4]+), which is shown in Figure 47 and found in the file Ch14Pr05_CuKa.xy online.
A total of 44 individual Bragg peaks are measurable up to 2 = 49.5° and these are listed in
Table 18 and also found in the file Ch14Pr05_CuKa.pks online. Peak positions, intensities,
and full widths at half maximum have been determined using a profile fitting procedure. The
observed Bragg angles are listed for the CuK1 component in the doublet, = 1.540593 Å.
a) Using TREOR, ITO and DICVOL perform ab initio indexing of the powder diffraction
pattern. Try to obtain solution in each of the three programs. Figure out a systematic error
using different orders of the same reflections. Indexing hint: the unit cell is relatively
large, therefore, increase maximum volume if no acceptable solution is found and use
only 20 lowest Bragg angle peaks.
b) Analyze the combinations of Miller indices of the observed Bragg reflections and
determine possible space groups describing symmetry of the material.
c) Perform the least squares refinement of the unit cell dimensions using all available data
without refining any kind of a systematic error. Analyze the differences between the
observed and calculated 2 and decide whether the refinement of zero shift or sample
displacement error is warranted. If it is, refine lattice parameters together with a zero shift
or a sample displacement error.
15
tea2Mo6O19, Cu K
12
Intensity, Y (10 counts)
9
3
0
10 20 30 40 50
Bragg angle, 2 (deg.)
Figure 47. The X-ray powder diffraction pattern of tea2Mo6O19 collected on a Scintag XDS2000 powder
diffractometer using CuK radiation. Numerical data are available in the file Ch14Pr05_CuKa.xy online.
Table 18. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the tea2Mo6O19 powder diffraction pattern collected using Cu K radiation in the
range 10 2 49.5° (see Figure 47). Numerical data are found in the file Ch14Pr05_CuKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
1000 10.241 0.085 52 35.282 0.075
Copyright © 2009 by Springer 102
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
182 11.573 0.070 6 35.425 0.075
65 12.376 0.073 24 35.567 0.075
30 16.408 0.076 24 36.419 0.075
30 16.986 0.076 24 37.259 0.075
4 19.393 0.050 4 37.531 0.075
163 20.615 0.074 41 37.798 0.075
14 22.217 0.074 16 39.282 0.071
20 23.297 0.074 19 39.667 0.071
17 24.933 0.074 8 40.316 0.071
73 25.523 0.074 5 41.842 0.082
155 26.286 0.074 9 41.972 0.082
6 26.479 0.074 55 42.355 0.082
22 26.851 0.074 4 42.747 0.082
3 28.138 0.074 3 43.698 0.082
78 28.991 0.074 9 43.824 0.082
13 29.842 0.074 24 45.242 0.081
28 30.004 0.074 6 45.725 0.081
20 30.508 0.074 15 47.671 0.081
45 31.153 0.074 3 48.911 0.081
32 32.427 0.074 7 49.244 0.081
2 34.830 0.075 5 49.357 0.081
a
Bragg angles are listed for the location of the CuK1 component in the doublet, = 1.540593 Å.
Solution:
a) Indexing
Estimation of sample displacement error:
The first peak is observed at 2 = 10.241. Its d-spacing is d1 = 8.63 Å. Second, third, and so on
orders of this peak should be observed at d2 = d1/2 (4.315 Å), d3 = d1/3 (2.877 Å), and so on. The
corresponding Bragg angles are 2 = 20.57, 31.06, and so on. These are the Bragg peaks
observed at 2 = 20.615, 31.153, and 41.972. The sample displacement (–0.075 mm,
goniometer radius 250 mm) can be determined assigning 001, 002, 003 and 004 indices,
respectively, to these four Bragg reflections and refining a unit cell parameter of a cubic unit cell.
Automatic indexing
A total of 20 lowest Bragg angle peaks were corrected for a sample displacement –0.05 mm
(goniometer radius 250 mm) and employed in all indexing attempts. Each indexing program
should result in a tetragonal solution. A weak peak at 2 = 28.138 was left unindexed in both
TREOR and ITO runs. No correct solution was found employing DICVOL, even with this weal
peak eliminated. The critical outputs are shown below
TREOR output
TOTAL NUMBER OF LINES = 20
A = 10.778474 0.000419 A ALFA = 90.000000 0.000000 DEG
B = 10.778474 0.000419 A BETA = 90.000000 0.000000 DEG
C = 14.263605 0.002796 A GAMMA = 90.000000 0.000000 DEG
UNIT CELL VOLUME = 1657.08 A**3
H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM.
1 0 1 0.008023 0.008024 -0.000001 10.278 10.278 8.5998 9999
Copyright © 2009 by Springer 103
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
1 1 0 0.010211 0.010214 -0.000004 11.599 11.601 7.6229 1815
0 0 2 0.011670 0.011665 0.000005 12.403 12.401 7.1304 646
2 0 0 0.020419 0.020429 -0.000009 16.431 16.435 5.3905 302
1 1 2 0.021871 0.021880 -0.000009 17.009 17.013 5.2086 297
2 1 1 0.028435 0.028452 -0.000017 19.416 19.422 4.5680 38
2 0 2 0.032087 0.032094 -0.000007 20.638 20.640 4.3002 1626
2 1 2 0.037193 0.037201 -0.000008 22.239 22.241 3.9941 138
2 2 0 0.040842 0.040858 -0.000015 23.319 23.323 3.8115 204
0 0 4 0.046661 24.950
2 0 3 0.046680 0.046676 0.000004 24.955 24.954 3.5652 165
3 0 1 0.048877 0.048881 -0.000005 25.545 25.546 3.4842 726
1 0 4 0.051769 26.303
2 1 3 0.051788 0.051783
0.000005 26.308 26.307 3.3848 1548
2 2 2 0.052537 0.052523
0.000014 26.501 26.497 3.3606 62
3 1 1 0.053995 0.053988
0.000006 26.873 26.871 3.3149 218
0.059183 28.160 3.1663 33
3 1 2 0.062745 0.062737 0.000008 29.013 29.011 3.0751 777
3 2 0 0.066395 0.066394 0.000002 29.864 29.864 2.9894 134
2 0 4 0.067090 30.024
2 2 3 0.067101 0.067105 -0.000004 30.026 30.027 2.9736 280
3 2 1 0.069318 0.069310 0.000008 30.530 30.528 2.9257 202
2 1 4 0.072197 31.173
3 0 3 0.072205 0.072212 -0.000007 31.175 31.177 2.8666 451
NUMBER OF OBS. LINES = 20
NUMBER OF CALC. LINES = 23
M( 20)= 138 AV.EPS.= 0.0000072
F 20 = 247.(0.002258, 36)
M( 20)= 138 AV.EPS.= 0.0000072
F 20 = 247.(0.002258, 36)
M CF. J.APPL.CRYST. 1(1968)108
F CF. J.APPL.CRYST. 12(1979)60
1 LINES ARE UNINDEXED
M-TEST= 138 UNINDEXED IN THE TEST= 1
ITO output
THE 8 MOST PROBABLE SOLUTIONS
LINES FIGUR LAT
Q(A) Q(B) Q(C) Q(D) Q(E) Q(F) INDXD MERIT TYP
86.1 49.2 86.1 0.0 0.0 0.0 19. 14.0 P
86.1 49.2 86.1 0.0 0.0 0.0 19. 14.0 P
86.1 49.2 86.1 0.0 0.0 0.0 19. 13.7 P
43.1 43.1 49.2 0.0 0.0 0.0 19. 12.2 C
91.9 43.1 58.6 17.1 13.0 0.0 20. 5.0 P
92.3 43.1 196.8 0.0 67.5 0.0 18. 10.2 P
86.2 49.2 92.3 30.7 43.0 0.0 19. 5.3 I
86.2 49.2 92.3 30.8 43.1 0.0 19. 5.3 I
THE DIRECT CONSTANTS OF THESE LATTICES
A B C ALFA BETA GAMMA VOLUME
10.7740 14.2554 10.7740 90.0000 90.0000 90.0000 1654.76
10.7740 14.2554 10.7740 90.0000 90.0000 90.0000 1654.76
10.7740 14.2554 10.7740 90.0000 90.0000 90.0000 1654.76
15.2368 15.2368 14.2554 90.0000 90.0000 90.0000 3309.53
10.4751 15.4578 13.3113 99.8484 95.1655 89.1176 2115.00
10.7518 15.2371 7.3627 90.0000 104.5073 90.0000 1167.75
11.1197 14.6664 11.0322 103.5821 104.3360 86.6665 1694.42
11.1206 14.6631 11.0343 103.6013 104.3674 86.6547 1694.13
****************************************************************************
* THE OBSERVED POSITIONS OF THE DIFFRACTION LINES ARE CORRECTED HERE *
* WITH A *ZERO-CORRECTION*, WHICH STANDS FOR THE SUM OF A REAL *
* ZEROPOINT ERROR PLUS A SPECIMEN DISPLACEMENT ERROR PLUS A TRANSPARENCY *
* ERROR. THE CORRECTION IS A CONSTANT OVER THE 2THETA RANGE. *
****************************************************************************
THE LATTICE WITH THE RECIPROCAL LATTICE CONSTANTS
86.15 49.21 86.15 0.00 0.00 0.00
IS PROBABLY TETRAGONAL WITH THE RECIPROCAL CONSTANTS
Copyright © 2009 by Springer 104
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
86.1 49.2 AND THE DIRECT CONSTANTS A= 10.77 C= 14.26
THE SYMMETRICAL LATTICE WITH THE CONSTANTS
86.139 49.205 CAN INDEX 19 FROM THE 20 LINES
ZEROSHIFT= -0.012 VOLUME= 1654.99
b) Possible space groups symmetry
The analysis of Miller indices points to a primitive lattice with the following systematic absences
0kl, k+l=2n (derived condition is h0l, h+l=2n) and hhl, l=2n. Thus, possible space group
symmetry is
P4/mnc or P4nc.
c) Refinement of lattice parameters
The least squares refinement of lattice parameters (WinCSD) using uncorrected Bragg angles
results in
a = 10.7825(6), c = 14.268(1) Å.
The plot of differences between the observed and calculated 2 is shown below. It indicates the
presence of a small systematic error. Note that some points (encircled) fall off from the 2 vs.
2 plot (weak or overlapped Bragg peaks, whose positions is difficult to determine accurately)
and they may be excluded from the refinement.
0.050
0.040
0.030
0.020
0.010
0.000
-0.010
-0.020
-0.030
-0.040 noshft
shift
-0.050
5 15 25 35 45
The least squares refinement of lattice parameters excluding marked reflections together with the
sample displacement error results in
a = 10.7745(6), c = 14.2574(9) Å, sample displacement = -0.074(5) mm.
Copyright © 2009 by Springer 105
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
6. Consider the X-ray powder diffraction pattern of MnV2O5 shown in Figure 48 and found in
the file Ch14Pr06_CuKa.xy online. A total of 53 individual Bragg peaks are measurable up
to 2 = 62° and these are listed in Table 19 and also found in the file Ch14Pr06_CuKa.pks
online. Peak positions, intensities, and full widths at half maximum have been determined
using a profile fitting procedure. The observed Bragg angles are listed for the K1 component
in the doublet, = 1.540593 Å.
a) Using TREOR, ITO and DICVOL perform ab initio indexing of the powder diffraction
pattern. Try to obtain solution in each of the three programs.
b) Analyze the combinations of Miller indices of all observed Bragg reflections and
determine possible space groups describing symmetry of the material.
c) Perform least squares refinement of the unit cell dimensions using all available data
without refining any kind of a systematic error. Analyze the differences between the
observed and calculated 2 and decide whether the data are affected by a zero shift or a
sample displacement error. If a systematic error is substantial, refine lattice parameters
together with a zero shift or a sample displacement error.
7
MnV2O5, Cu K
6
Intensity, Y (10 counts)
5
3
0
10 20 30 40 50 60 70
Bragg angle, 2 (deg.)
Figure 48. The X-ray powder diffraction pattern of MnV2O5 collected on a Scintag XDS2000 powder
diffractometer using CuK radiation. Numerical data are available in the file Ch14Pr06_CuKa.xy online.
Table 19. Relative integrated intensities (I/I0), Bragg angles and full widths at half maximum (FWHM) of
Bragg peaks observed in the MnV2O5 powder diffraction pattern collected using Cu K radiation in the
range 12 2 62° (see Figure 48). Numerical data are found in the file Ch14Pr06_CuKa.pks.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
36 12.595 0.062 82 47.584 0.123
261 15.710 0.124 363 47.828 0.123
681 18.152 0.113 107 48.546 0.123
281 19.801 0.109 125 49.100 0.123
Copyright © 2009 by Springer 106
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
I/I0 2 (deg)a FWHM (deg) blank I/I0 2 (deg) a FWHM (deg)
519 24.091 0.113 464 49.335 0.123
307 25.367 0.113 106 49.720 0.123
31 26.049 0.113 484 50.890 0.123
592 27.630 0.113 10 51.336 0.123
1000 28.520 0.113 28 52.091 0.123
988 29.972 0.113 88 52.774 0.123
829 30.912 0.113 13 53.593 0.123
443 31.715 0.113 51 54.474 0.123
578 31.935 0.113 23 55.132 0.123
172 34.542 0.111 29 55.407 0.123
786 34.856 0.111 320 55.983 0.123
78 35.778 0.111 63 57.063 0.131
51 36.788 0.111 182 57.339 0.131
229 37.673 0.111 35 57.698 0.131
34 38.157 0.111 41 57.965 0.131
27 39.268 0.152 325 58.526 0.131
136 40.215 0.152 116 59.021 0.131
456 41.035 0.152 296 59.156 0.131
314 42.378 0.152 124 59.367 0.131
40 44.182 0.126 148 60.186 0.131
63 44.630 0.126 78 61.212 0.131
123 44.877 0.126 15 61.610 0.131
123 45.631 0.126
a
Bragg angles are listed for the location of the CuK1 component in the doublet, = 1.540593 Å.
Solution:
a) Indexing
Each indexing attempt should result in an orthorhombic solution. Using 34 peaks below 51 2,
only ITO results in an acceptable unit cell. The lowest Bragg angle peak, however, is left
unindexed. Considering that it is relatively weak, we may assume that it belongs to an impurity,
especially because all other reflections fit into the found unit cell quite well with M20 = 83. After
this peak was eliminated, both TREOR and DICVOL result in the same unit cell. The critical
outputs are shown below.
ITO15 output
THE 8 MOST PROBABLE SOLUTIONS
LINES FIGUR LAT
Q(A) Q(B) Q(C) Q(D) Q(E) Q(F) INDXD MERIT TYP
104.9 78.6 777.2 0.0 0.0 0.0 19. 70.3 P
...
104.9 78.6 777.2 0.0 0.0 0.0 19. 56.5 P
77.9 26.1 852.7 0.0 0.0 0.0 19. 14.3 P
104.8 78.6 123.9 0.0 7.9 0.0 19. 12.4 P
THE DIRECT CONSTANTS OF THESE LATTICES
A B C ALFA BETA GAMMA VOLUME
9.7659 11.2792 3.5870 90.0000 90.0000 90.0000 395.11
...
9.7659 11.2793 3.5870 90.0000 90.0000 90.0000 395.11
Copyright © 2009 by Springer 107
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
11.3284 19.5650 3.4245 90.0000 90.0000 90.0000 759.00
9.7731 11.2789 8.9907 90.0000 91.9865 90.0000 990.44
*********************************************************************
* THIS PROGRAM GIVES A NUMBER OF SUGGESTIONS THAT MAY HELP YOU TO *
* FIND THE UNIT CELL THAT EXPLAINS YOUR EXPERIMENTAL DATA. HOWEVER *
* *
* WWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWW *
* W W *
* W IT IS ENTIRELY THE USERS RESPONSIBILITY TO DECIDE W *
* W WHETHER ANY OF THE SUGGESTED UNIT CELLS IS THE W *
* W CORRECT CELL. W *
* W W *
* WWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWWW *
* *
*********************************************************************
THE BEST SOLUTION IS NOW USED TO TRY AND INDEX ALL GIVEN LINES
SOLUTION NR. 1
104.85 78.60 777.23 0.00 0.00 0.00 19. 70.3
************************************************
* USE THE LIST TO FIND SYSTEMATIC ABSENCES *
************************************************
LIST OF ALL OBSERVED AND CALCULATED LINES UP TO THE 32ST.
IF THE TWOTHETAS DIFFER MORE THAN 0.054 DEGREES,
A BLANK LINE IS INSERTED.
TWOTHETA D H K L Q
7.831 11.280 0 1 0 78.6
9.047 9.767 1 0 0 104.8
11.977 7.384 1 1 0 183.4
12.596 7.022 *OBSERVED 202.8 18 XXXXXXXX ! unindexed
15.700 5.640 0 2 0 314.4
15.711 5.636 *OBSERVED 314.8 50
18.149 4.884 1 2 0 419.2
18.152 4.883 2 0 0 419.3
18.153 4.883 *OBSERVED 419.4 81
19.796 4.481 2 1 0 497.9
19.802 4.480 *OBSERVED 498.3 52
23.644 3.760 0 3 0 707.4
24.087 3.692 2 2 0 733.8
24.092 3.691 *OBSERVED 734.0 71
24.803 3.587 0 0 1 777.3
25.363 3.509 1 3 0 812.2
25.368 3.508 *OBSERVED 812.5 54
26.048 3.418 0 1 1 855.9
26.050 3.418 *OBSERVED 856.0 17
26.451 3.367 1 0 1 882.2
27.374 3.255 3 0 0 943.6
27.627 3.226 1 1 1 960.8
27.631 3.226 *OBSERVED 961.0 76
28.514 3.128 3 1 0 1022.2
Copyright © 2009 by Springer 108
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
28.521 3.127 *OBSERVED 1022.6 99
29.490 3.027 0 2 1 1091.7
29.970 2.979 2 3 0 1126.8
29.973 2.979 *OBSERVED 1126.9 98
30.907 2.891 1 2 1 1196.6
30.909 2.891 2 0 1 1196.7
30.913 2.890 *OBSERVED 1197.0 90
31.706 2.820 0 4 0 1257.6
31.710 2.819 3 2 0 1258.0
31.716 2.819 *OBSERVED 1258.4 65
31.934 2.800 2 1 1 1275.3
31.936 2.800 *OBSERVED 1275.4 75
33.037 2.709 1 4 0 1362.5
34.533 2.595 0 3 1 1484.7
34.543 2.595 *OBSERVED 1485.6 41
34.847 2.573 2 2 1 1511.1
34.857 2.572 *OBSERVED 1511.9 87
35.771 2.508 1 3 1 1589.6
35.779 2.508 *OBSERVED 1590.2 27
36.479 2.461 3 3 0 1651.0
36.775 2.442 2 4 0 1677.0
36.781 2.442 4 0 0 1677.4
36.789 2.441 *OBSERVED 1678.1 22
37.271 2.411 3 0 1 1720.9
37.664 2.386 4 1 0 1756.0
37.674 2.386 *OBSERVED 1756.9 47
38.145 2.357 3 1 1 1799.5
38.158 2.357 *OBSERVED 1800.6 18
39.269 2.292 *OBSERVED 1902.8 16
39.282 2.292 2 3 1 1904.1
39.932 2.256 0 5 0 1965.0
40.216 2.241 *OBSERVED 1991.9 36
40.215 2.241 4 2 0 1991.9
40.667 2.217 0 4 1 2034.9
40.671 2.217 3 2 1 2035.3
41.030 2.198 1 5 0 2069.9
41.036 2.198 *OBSERVED 2070.4 66
41.749 2.162 1 4 1 2139.8
42.372 2.131 3 4 0 2201.2
42.379 2.131 *OBSERVED 2201.8 55
44.183 2.048 *OBSERVED 2383.7 19
44.190 2.048 2 5 0 2384.4
44.194 2.048 4 3 0 2384.9
44.616 2.029 3 3 1 2428.3
44.631 2.029 *OBSERVED 2429.8 24
44.867 2.019 2 4 1 2454.3
44.872 2.018 4 0 1 2454.8
Copyright © 2009 by Springer 109
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
44.878 2.018 *OBSERVED 2455.4 34
45.625 1.987 4 1 1 2533.4
45.632 1.986 *OBSERVED 2534.1 34
46.452 1.953 5 0 0 2621.0
47.185 1.925 5 1 0 2699.6
47.580 1.910 0 5 1 2742.4
47.585 1.909 *OBSERVED 2742.8 28
47.827 1.900 4 2 1 2769.2
47.829 1.900 *OBSERVED 2769.4 59
48.379 1.880 0 6 0 2829.7
48.539 1.874 1 5 1 2847.2
48.547 1.874 *OBSERVED 2848.1 32
49.093 1.854 3 5 0 2908.6
49.101 1.854 *OBSERVED 2909.4 34
49.326 1.846 1 6 0 2934.5
49.331 1.846 4 4 0 2935.1
49.334 1.846 5 2 0 2935.4
49.336 1.846 *OBSERVED 2935.6 67
THERE ARE 1 UNINDEXED LINES AMONGST THE FIRST 20 INDEXED LINES.
SOLUTION NR. 1
104.84 78.60 777.35 0.00 0.00 0.00 20. 83.1
ZEROSHIFT= -0.0006 DEGREES TWOTHETA
THE DIRECT CONSTANTS OF THESE LATTICES
A B C ALFA BETA GAMMA VOLUME
9.7663 11.2792 3.5867 90.0000 90.0000 90.0000 395.09
TREOR output
NUMBER OF SINGLE INDEXED LINES = 26
TOTAL NUMBER OF LINES = 33
A = 11.278287 0.000706 A ALFA = 90.000000 0.000000 DEG
B = 9.765305 0.000680 A BETA = 90.000000 0.000000 DEG
C = 3.585879 0.000242 A GAMMA = 90.000000 0.000000 DEG
UNIT CELL VOLUME = 394.93 A**3
H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM.
2 0 0 0.018666 0.018658 0.000008 15.705 15.702 5.6380 2613
2 1 0 0.024880 18.151
0 2 0 0.024893 0.024888 0.000005 18.156 18.154 4.8821 6808
1 2 0 0.029547 0.029552 -0.000006 19.796 19.798 4.4812 2814
2 2 0 0.043546 0.043546 0.000000 24.090 24.090 3.6913 5189
3 1 0 0.048209 0.048203 0.000006 25.367 25.365 3.5082 3065
1 0 1 0.050791 0.050808 -0.000017 26.049 26.053 3.4179 309
1 1 1 0.057020 0.057030 -0.000010 27.630 27.632 3.2258 5920
1 3 0 0.060675 0.060662 0.000013 28.520 28.517 3.1271 9999
3 2 0 0.066865 0.066869 -0.000004 29.972 29.973 2.9789 9882
2 1 1 0.071021 0.071023 -0.000002 30.912 30.912 2.8904 8292
0 2 1 0.071031 30.914
4 0 0 0.074633 31.708
2 3 0 0.074663 0.074656 0.000008 31.715 31.713 2.8190 4432
1 2 1 0.075676 0.075695 -0.000020 31.935 31.939 2.8001 5781
3 0 1 0.088145 0.088124 0.000021 34.542 34.538 2.5945 1718
2 2 1 0.089704 0.089689 0.000015 34.856 34.853 2.5718 7863
3 1 1 0.094356 0.094346 0.000010 35.778 35.776 2.5076 779
4 2 0 0.099521 36.778
0 4 0 0.099572 0.099551 0.000021 36.788 36.784 2.4411 508
1 4 0 0.104244 0.104216 0.000029 37.673 37.668 2.3857 2288
1 3 1 0.106840 0.106805 0.000035 38.157 38.151 2.3566 338
3 2 1 0.112903 0.113012 -0.000109 39.268 39.288 2.2924 274
2 4 0 0.118186 0.118209 -0.000023 40.215 40.219 2.2406 1361
Copyright © 2009 by Springer 110
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5 1 0 0.122846 0.122836 0.000010 41.035 41.033 2.1977 4555
4 3 0 0.130643 0.130630 0.000012 42.378 42.376 2.1311 3143
5 2 0 0.141435 0.141502 -0.000067 44.182 44.193 2.0482 402
3 4 0 0.141532 44.198
3 3 1 0.144171 0.144122 0.000049 44.630 44.622 2.0287 633
4 2 1 0.145664 44.873
0 4 1 0.145688 0.145694 -0.000006 44.877 44.878 2.0181 1233
1 4 1 0.150362 0.150359 0.000003 45.631 45.631 1.9865 1231
5 0 1 0.162746 0.162757 -0.000011 47.584 47.586 1.9094 815
2 4 1 0.164321 0.164352 -0.000032 47.828 47.833 1.9002 3624
5 1 1 0.168991 0.168979 0.000012 48.546 48.544 1.8738 1071
5 3 0 0.172630 0.172612 0.000018 49.100 49.097 1.8539 1248
6 1 0 0.174146 49.330
4 4 0 0.174182 0.174184 -0.000002 49.335 49.335 1.8456 4635
2 5 0 0.174207 49.339
4 3 1 0.176738 0.176773 -0.000035 49.720 49.725 1.8322 1059
0 0 2 0.184594 0.184572 0.000022 50.890 50.887 1.7928 4838
NUMBER OF OBS. LINES = 33
NUMBER OF CALC. LINES = 41
M( 20)= 94 AV.EPS.= 0.0000179
F 20 = 154.(0.003723, 35)
M( 30)= 83 AV.EPS.= 0.0000193
F 30 = 152.(0.003661, 54)
M( 33)= 81 AV.EPS.= 0.0000193
F 33 = 156.(0.003595, 59)
M CF. J.APPL.CRYST. 1(1968)108
F CF. J.APPL.CRYST. 12(1979)60
0 LINES ARE UNINDEXED
DICVOL output
O R T H O R H O M B I C S Y S T E M
DIRECT PARAMETERS : A= 11.27806 B= 9.76507 C= 3.58600 VOLUME= 394.93
STANDARD DEVIATIONS : 0.00077 0.00071 0.00027
H K L DOBS DCAL DOBS-DCAL QOBS QCAL 2TH.OBS 2TH.CAL DIF.2TH.
2 0 0 5.63620 5.63903 -0.00283 0.031480.03145 15.710 15.702 0.008
0 2 0 4.88309 4.88254 0.00055 0.041940.04195 18.152 18.154 -0.002
2 1 0 4.88329 -0.00021 0.04193 18.151 0.001
1 2 0 4.47999 4.48067 -0.00067 0.049820.04981 19.801 19.798 0.003
2 2 0 3.69105 3.69118 -0.00012 0.073400.07340 24.091 24.090 0.001
3 1 0 3.50821 3.50835 -0.00014 0.081250.08124 25.367 25.366 0.001
1 0 1 3.41788 3.41741 0.00047 0.085600.08563 26.049 26.053 -0.004
1 1 1 3.22579 3.22559 0.00021 0.096100.09611 27.630 27.632 -0.002
1 3 0 3.12712 3.12738 -0.00026 0.102260.10224 28.520 28.518 0.002
3 2 0 2.97885 2.97871 0.00014 0.112690.11271 29.972 29.973 -0.001
0 2 1 2.89037 2.89022 0.00015 0.119700.11971 30.912 30.914 -0.002
2 1 1 2.89038 0.00000 0.11970 30.912 0.000
2 3 0 2.81900 2.81908 -0.00008 0.125840.12583 31.715 31.714 0.001
4 0 0 2.81952 -0.00052 0.12579 31.709 0.006
1 2 1 2.80008 2.79975 0.00033 0.127540.12757 31.935 31.939 -0.004
3 0 1 2.59448 2.59481 -0.00032 0.148560.14852 34.542 34.538 0.004
2 2 1 2.57183 2.57206 -0.00024 0.151190.15116 34.856 34.853 0.003
3 1 1 2.50763 2.50778 -0.00015 0.159030.15901 35.778 35.776 0.002
0 4 0 2.44107 2.44127 -0.00019 0.167820.16779 36.788 36.785 0.003
4 2 0 2.44165 -0.00057 0.16774 36.779 0.009
1 4 0 2.38574 2.38601 -0.00027 0.175690.17565 37.673 37.669 0.004
1 3 1 2.35658 2.35697 -0.00038 0.180070.18001 38.157 38.151 0.006
3 2 1 2.29243 2.29133 0.00110 0.190290.19047 39.268 39.288 -0.020
2 4 0 2.24060 2.24033 0.00027 0.199190.19924 40.215 40.220 -0.005
5 1 0 2.19770 2.19774 -0.00004 0.207040.20704 41.035 41.034 0.001
4 3 0 2.13111 2.13117 -0.00006 0.220190.22017 42.378 42.377 0.001
3 4 0 2.04819 2.04744 0.00075 0.238370.23855 44.182 44.199 -0.017
5 2 0 2.04766 0.00052 0.23850 44.194 -0.012
3 3 1 2.02866 2.02900 -0.00034 0.242990.24290 44.630 44.622 0.008
0 4 1 2.01807 2.01802 0.00005 0.245540.24556 44.877 44.878 -0.001
4 2 1 2.01823 -0.00016 0.24550 44.873 0.004
1 4 1 1.98646 1.98647 -0.00001 0.253420.25342 45.631 45.631 0.000
Copyright © 2009 by Springer 111
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
5 0 1 1.90939 1.90931 0.00008 0.274290.27431 47.584 47.586 -0.002
2 4 1 1.90021 1.90002 0.00020 0.276950.27700 47.828 47.833 -0.005
5 1 1 1.87377 1.87383 -0.00005 0.284820.28480 48.546 48.544 0.002
5 3 0 1.85392 1.85398 -0.00006 0.290950.29093 49.100 49.098 0.002
2 5 0 1.84564 1.84547 0.00017 0.293570.29362 49.335 49.340 -0.005
4 4 0 1.84559 0.00005 0.29358 49.336 -0.001
6 1 0 1.84579 -0.00016 0.29352 49.331 0.004
4 3 1 1.83224 1.83205 0.00020 0.297870.29794 49.720 49.726 -0.006
0 0 2 1.79283 1.79300 -0.00017 0.311120.31106 50.890 50.885 0.005
* NUMBER OF LINES
.- INPUT DATA = 33
.- CALCULATED = 59
* MEAN ABSOLUTE DISCREPANCIES
<Q> =0.3305E-04
<DELTA(2-THETA)> =0.3698E-02
MAX. ERROR ACCEPTED (DEG. 2-THETA) =0.4500E-01
* FIGURES OF MERIT
1.- M( 33) = 79.8 (REF. 4)
2.- F( 33) = 151.3(0.0037, 59) (REF. 5)
b) Possible space groups symmetry
Note that all three indexing program result in the same unit cell, however, selection of axes by
ITO is different. The following analysis is performed using the following assignment of axes:
a=11.278, b=9.765, c=3.586 Å. The analysis of Miller indices points to a primitive lattice with
the following additional systematic absences 0kl, k=2n and h0l, h+l=2n. Thus, possible space
groups symmetry include:
Pbnm or Pbn21
Considering the simplicity of the metal oxide formula, the centrosymmetric space group is highly
probable. In a standard setting, this space group is Pnma, which is obtained by the following
transformation of axis:
a s = bi ,
bs = ci,
cs = ai,
where subscripts s and i refer to the standard and as indexed selection of the axes, respectively.
The unit cell dimensions in a standard setting are a=9.765, b=3.586, c=11.278 Å. Note that the
standard setting of the non-centrosymmetric group is Pna21 and, therefore, the corresponding
transformation of axes is different from the centrosymmetric case.
c) Refinement of lattice parameters
The least squares refinement of lattice parameters for Pnma setting (WinCSD) without accounting
for a systematic error results in
a = 9.7657(3), b = 3.58578(9), c = 11.2786(3) Å.
The plot of the differences between the observed and calculated 2 is shown below.
It indicates the presence of very small systematic error, which is hardly visible in the scale of the
figure. Note that two points (encircled) fall off from the 2 vs. 2 plot (weak Bragg peak,
Copyright © 2009 by Springer 112
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
whose positions is difficult to determine accurately) and they may be excluded from the
refinement.
0.050
0.040
0.030
0.020
0.010
0.000
-0.010
-0.020
-0.030
-0.040
noshft
shift
-0.050
5.000 10.000 15.000 20.000 25.000 30.000 35.000 40.000 45.000 50.000
The least squares refinement of lattice parameters together with the sample displacement error
results in
a = 9.7666(4), b = 3.5861(1), c = 11.2795(4) Å,
and practically negligible sample displacement correction: 0.013(4) mm (goniometer radius 250
mm).
Copyright © 2009 by Springer 113
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Chapters 15-251
1. The compound Mn5Si3O12 crystallizes in the space group Iad with lattice parameter a =
11.85 Å. The measured gravimetric density, = 4.4 g/cm3. Calculate the number of formula
units in the unit cell and the number of atoms of each kind. Make a suggestion, which sites
can be occupied by the different types of atoms in this unit cell.
Solution:
Number of formula units Z = 8
The overall content of the unit cell is Mn40Si24O96
Given the multiplicities of site positions in the space groups Ia3d:
Si atoms can be located in 24(d) or 24(c);
Mn atoms can be located in 24(d) or 24(c). Since both sites have no free parameters, if 24(d)
is occupied by Si, then Mn may be located in 24(c) and vice versa. The total number of Mn
atoms is 40. Thus, one of the 16-fold sites should be also occupied by Mn atoms. This may be
16(a) or 16(b);
Oxygen may occupy a single 96(h) site, or two 48(g) or 48(f), or three 32(e) sites in this
space group symmetry.
1
Instrumental parameters for GSAS Rietveld refinement are available online in files InstCuKa.prm and
InstMoKa.prm.
Copyright © 2009 by Springer 114
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
2. The compound Co2Mn3O8 crystallizes in the space group Pmn21 with lattice parameters a =
5.743, b = 4.915 and c = 9.361 Å. Assuming a reasonable density of a 3d-metal oxide (3 to 6
g/cm3), find the number of formula units in the unit cell and calculate the x-ray density of the
material.
Solution:
Given the reasonable density in the range 3 - 6 g/cm3, the number of formula units (Co2Mn3O8) is
Z = 2. The calculated gravimetric density (x-ray density) is calc = 5.16 g/cm3.
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3. Cobalt oxide, CoO, crystallizes in the cubic crystal system, space group Fmm, a = 4.26 Å.
The measured gravimetric density of the oxide is = 6.438 g/cm3. Using only these data,
solve its crystal structure (find positions of atoms that make chemical and physical sense and
have reasonable interatomic distances).
Solution:
From the unit cell dimension and gravimetric density, Z = 4. Hence, Co atoms occupy 4(a): 0,0,0;
and O atoms are in 4(b), 1/2,1/2,1/2. Alternative model, where Co atoms are in 4(b): 1/2,1/2,1/2;
and O atoms are in 4(a), 0,0,0 is identical to the previous model with respect to the 1/2,1/2,1/2
shift. The model of the crystal structure is shown in Figure 49.
Figure 49. The model of the crystal structure of CoO shown as packing of the [CoO6] octahedra along the
[111] direction.
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4. The compound TaMn2O3 crystallizes in the hexagonal crystal system and belongs to the
space group P6/mmm with a = 5.321, c = 3.578 A. The measured gravimetric density of the
material is = 6.30 g/cm3. Using only these data, solve the crystal structure of the material
(find positions of atoms that make chemical and physical sense and have reasonable
interatomic distances).
Solution:
From the unit cell dimensions and gravimetric density, Z = 1. Therefore, Ta can occupy either
1(a): 0,0,0 or 1(b): 0,0,1/2. The two sites differ only by the shift of the origin of coordinates. Let’s
choose the former: Ta in 1(a).
Mn cannot be in the 2(e), 0,0,z because it results in the distances Mn-Ta and Mn-Mn that are too
short (the largest distances are for z = ~1/3: (Mn-Ta) = (Mn-Mn) = 1/3a = ~1.19 Å. Hence, Mn
atoms can occupy either 2(c): 1/3,2/3,0 (Mn1) or 2(d): 1/3,2/3,1/2 (Mn2) positions.
Oxygen atoms can be in 3(f): 1/2,0,0 (O1) or 3(g): 1/2,0,1/2 (O2). O1 is too close to Mn1 and O2
is too close to Mn2 (1.54 Å). Hence, one of the pairs: Mn1 and O2 or Mn2 and O1 should be
selected, thus resulting in the satisfactory distances. The latter pair is preferred as O and Ta are
located in the same plane resulting in 2.66 Å Ta-O2 distances with Ta-Mn1 distance of 3.56 Å,
while in the former Ta is basically surrounded by Mn atoms at 3.07 Å with Ta-O2 distance 3.21
Å (Fig. 2b). Thus, the model containing Ta, Mn1 and O2 (Figure 50a) looks realistic, unlike Ta,
Mn2, and O1 shown in Figure 50b.
Figure 50. The two models of the crystal structure of the TaMn2O3: correct – Ta, Mn1 and O2 (a) and
incorrect – Ta, Mn2 and O1 (b).
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5. Hexamethylenetetramine molecule, C6H12N4 (hmta), has the configuration of a tetrahedron,
where the corners are occupied by nitrogen atoms, which are bonded with each other by
means of six methylene, CH2, groups located above the mid points of the edges of the
tetrahedron as shown in Figure 51. The compound crystallizes in the cubic crystal system,
space group I3m, a = 7.05 Å. The measured gravimetric density is = 1.33 g/cm3.
Assuming that the tetrahedron is ideal and that the C–N distances are 1.49 Å, solve this
crystal structure (i.e. determine the coordinates of non-hydrogen atoms) using data provided
above including both the symmetry of the lattice and hmta molecule. To simplify
calculations, consider the following: the distance from the center (X) of the tetrahedron to
the C atoms is X–C = 1.72 Å, and to the N atoms, X–N = 1.49 Å.
Figure 51. The molecule of hexamethylenetetramine, shown using displacement ellipsoids of carbon and
nitrogen atoms.
Solution:
From the gravimetric density, molecular formula and unit cell dimensions, Z = 2. Therefore, the
hmta molecule should preserve its local symmetry, which is43m, and its center should be
located in the origin of coordinates with the same point symmetry. The multiplicity of this site,
2(a), is two – the same as Z. Thus, the molecule should be placed with its center (no atom there)
in the 2(a) site in such way that N-atoms are located on the three-fold axes and C atoms are
positioned on the4 axes.
From the distance X – N, xa3 = 1.49 x = 0.122; 8 N in 8(c), xxx, x = 0.122.
From the distance X – C, xa = 1.72 x = 0.244; 12 C in 12 (e), x00, x = 0.244.
The packing of hmta molecules in the unit cell is shown in Figure 52.
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Figure 52. The model of the crystal structure of hexamethylenetetramine.
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6. Consider the powder diffraction pattern shown in Figure 53, which was collected from an
intermetallic compound with the approximate stoichiometry SrSi2 on a Rigaku TTRAX
rotating anode powder diffractometer using Mo K radiation. The density of the alloy was
measured in a pycnometer and it is 3.3(1) g/cm3. The pattern was indexed and the possible
space groups were established during solution of Problem 3 in Chapter 14. Experimental
data are found in the data files Ch25Pr06_MoKa.xy and Ch25Pr06_MoKa.raw online.
Solve this crystal structure from first principles.
Figure 53. Powder diffraction pattern collected from a ground powder with the approximate stoichiometry
SrSi2 on a rotating anode Rigaku TTRAX diffractometer. The data were collected with a step 2 = 0.015°.
Solution:
Unit cell dimensions and possible space groups were established during solution of Problem 3 in
Chapter 14. If our reasoning about space groups was incorrect, and either or both 003 and 005
have non-zero intensities, then no reflections are forbidden and we will need to test one or more
from the following space groups: P23, Pm, P432, P3m, or Pmm. If one of the two groups
(P4132 or P4332) characterizes the symmetry of the material, they are enantiomorphous and
indistinguishable from powder diffraction.
a) Full pattern decomposition, unit cell content
Le Bail’s full pattern decomposition converges to Rp = 5.28 %, Rwp = 7.59 %, 2 = 1.67 and Rexp
= 5.89 % and results in 107 individual |Fhkl|2, which are listed in Table 20. The refined unit cell
parameter a = 6.5410(1) Å with Rietica’s sample displacement of -0.17.
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Table 20. Individual observed structure factors determined from Le Bail’s full pattern decomposition.
h k l |Fhkl|2 Error h k l |Fhkl|2 Error h k l |Fhkl|2 Error
0 1 1 1106 10 0 1 6 3863 55 0 0 8 202 5
1 1 1 1271 16 1 1 6 3215 29 0 1 8 246 6
0 1 2 19538 54 2 3 5 4367 40 0 4 7 189 4
1 1 2 14493 51 0 2 6 1594 31 2 5 6 172 4
0 2 2 1275 21 0 4 5 653 11 1 1 8 1525 21
1 2 2 2313 24 1 2 6 803 13 1 4 7 1699 24
0 1 3 1135 16 3 4 4 640 10 4 5 5 1713 24
1 1 3 8641 53 1 4 5 2850 37 3 3 7 2309 40
2 2 2 7776 86 3 3 5 664 15 0 2 8 81 2
0 2 3 3438 35 2 2 6 8962 97 4 4 6 94 2
1 2 3 10713 48 0 3 6 5646 48 1 2 8 1320 19
0 0 4 24543 210 2 4 5 5303 45 2 4 7 1696 25
0 1 4 1872 20 1 3 6 2077 30 3 5 6 614 11
2 2 3 1879 20 4 4 4 7610 134 0 6 6 594 13
0 3 3 3477 34 2 3 6 488 11 2 2 8 980 21
1 1 4 3305 32 0 1 7 1767 22 0 3 8 1 0
1 3 3 8324 68 0 5 5 2165 28 1 6 6 1 0
0 2 4 7 0 3 4 5 1990 25 0 5 7 1638 23
1 2 4 7888 50 1 1 7 2602 35 1 3 8 1384 19
2 3 3 2899 38 1 5 5 3156 43 3 4 7 1457 20
2 2 4 0 0 0 4 6 12 0 1 5 7 1724 25
0 3 4 937 19 0 2 7 1861 25 5 5 5 1862 26
0 1 5 3181 27 1 4 6 2297 31 2 6 6 3938 62
1 3 4 3364 29 1 2 7 878 14 2 3 8 2506 30
1 1 5 3189 39 2 5 5 1174 19 4 5 6 2880 35
3 3 3 3638 45 3 3 6 922 14 2 5 7 2042 28
0 2 5 7577 47 2 4 6 165 4 0 4 8 2131 42
2 3 4 7564 47 2 2 7 153 4 1 4 8 123 3
1 2 5 2445 29 4 4 5 132 3 3 6 6 145 3
0 4 4 12041 140 0 3 7 3211 55 4 4 7 116 2
1 4 4 271 7 1 3 7 1554 23 0 1 9 754 14
2 2 5 231 5 3 5 5 1723 26 3 3 8 807 15
0 3 5 1568 24 0 5 6 2807 37 1 1 9 568 11
3 3 4 1450 22 3 4 6 2453 32 3 5 7 594 12
1 3 5 1292 21 1 5 6 963 15 2 4 8 513 11
2 4 4 2314 39 2 3 7 947 15
Molecular mass of the formula unit is Sr + 2 Si = 87.62 + 228.09 = 143.8 a.m.u.
Using Eq. 6.4 we find that there are 3.9 4 “SrSi2” formula units in the unit cell.
b) Structure solution
The following sites are available in the space group P4132 to accommodate 4Sr and 8Si:
4(a): 3/8, 3/8, 3/8
4(b): 7/8, 7/8, 7/8
8(c): x,x,x
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In this case, the location of the heavy atom (Sr) is obvious: 4(a) or 4(b) sites, which are identical
to one another. If we employ direct or Patterson technique, it is easy to find that both also yield a
heavy atom in one of these sites.
After Sr is placed in 4(a), the corresponding RF = 34.5 %, which is quite low. The following
Fourier map yields one Si atom in 8(c) with x = 0.087. When this atom is included in the
calculation of phases, the RF = 21.4 %. The subsequent Fourier map confirms both atoms and the
new xSi = 0.0806. The recalculated RF lowers to 18.2 % and another Fourier map further reduces
xSi to 0.0780. RF lowers once more to 17.9 % and a fourth Fourier map does not change the
coordinate parameter of Si in 8(c). The next strongest peak on the Fourier map is ~1/7 that of Si,
thus no more atoms are present in the unit cell.
The shortest interatomic distances are as follows:
Sr – Sr: 4.01 Å
Sr – Si: 3.26 Å
Si – Si: 2.39 Å
All of which are normal, and we conclude that the feasible model of the crystal structure has been
found. It is shown Figure 54. The solution should be completed by employing Rietveld
refinement, which is one of the problems suggested later (Problem 10).
Figure 54. The model of the crystal structure of SrSi2.
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7. Consider the pattern from Problem 1 in Chapter 14 (Figure 43). Powder diffraction data were
collected in the range of Bragg angles from 20 to 140° on an HZG-4a powder diffractometer
using filtered Cu K radiation. The data are found in the files Ch25Pr07_CuKa.xy and
Ch25Pr07_CuKa.raw online in the supplementary information accompanying this book.
Solve the crystal structure of this material, knowing that its gravimetric density (measured
pycnometrically) is = 7.7 g/cm3.
Solution:
The pattern has been indexed earlier; possible space groups are F3c or Fmc, and the unit cell
dimension is a = 11.3768 Å. After considering the gravimetric density of the material and the
mass of the formula unit (M = 1La + 11.6Ni +1.4Ge = 138.91 + 11.658.69 + 1.428.09 = 859.04
a.m.u), the content of the unit cell (number of formula units) is Z = 7.95 8. Thus, we are looking
for 8 La atoms and 104 Ni plus Ge atoms (the latter two may be statistically distributed in the
corresponding lattice sites because of the similarity of the atomic volumes of Ni and Ge).
The following sites in the highest symmetry space group (Fmc) are available to accommodate
various atoms in the unit cell:
8(a): 1/4, 1/4, 1/4
8(b): 0, 0, 0
24(c): 1/4, 0, 0
24 (d): 0, 1/4, 1/4
48(e): x, 0, 0
48(f): x, 1/4, 1/4
64(g): x, x, x
96(h): 1/4, x, x
96(i): 0, y, z
Thus, it appears that one eight-fold site is occupied by La. A variety of sites may be occupied by
Ni and/or Ge to fulfill the 1:13 stoichiometry.
b) Full pattern decomposition
Using lattice parameter listed above and space group Fmc, Le Bail’s full pattern decomposition
converges at Rp = 5.52 %, Rwp = 7.16 %, 2 = 0.82 and Rexp = 7.89 %, and results in 70 individual
|Fhkl|2, which are listed in Table 21. The refined unit cell parameter a = 11.3796(1) Å with a
sample displacement of -0.06.
Table 21. Individual observed structure factors determined from Le Bail’s full pattern decomposition.
h k l |Fhkl|2 Error h k l |Fhkl|2 Error h k l |Fhkl|2 Error
0 2 2 150 3 2 4 8 42 55 0 0 12 1195 18
2 2 2 758 10 4 6 6 56 29 4 8 8 848 11
0 0 4 1226 17 1 3 9 935 40 1 5 11 48 1
0 2 4 2488 16 4 4 8 2929 31 0 2 12 241 4
2 2 4 5323 26 0 0 10 599 11 2 2 12 750 9
0 4 4 115 3 0 6 8 559 13 4 6 10 605 7
1 3 5 4391 20 0 2 10 1154 10 3 5 11 154 2
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h k l |Fhkl|2 Error h k l |Fhkl|2 Error h k l |Fhkl|2 Error
0 0 6 1221 12 2 6 8 1095 37 5 7 9 141 2
2 4 4 1351 13 1 5 9 701 15 0 4 12 0 0
0 2 6 2310 21 2 2 10 827 97 0 8 10 77 1
2 2 6 66 2 6 6 6 608 48 2 4 12 80 1
4 4 4 3106 40 3 5 9 1294 45 6 8 8 74 1
0 4 6 2169 22 0 4 10 177 30 2 8 10 116 2
2 4 6 1319 13 4 6 8 182 134 1 7 11 56 1
1 3 7 27 1 2 4 10 531 11 6 6 10 63 1
0 0 8 5283 69 0 8 8 0 22 4 4 12 373 5
0 2 8 1473 15 1 3 11 500 28 1 3 13 315 4
4 4 6 1179 12 1 7 9 450 25 3 7 11 340 4
0 6 6 444 7 2 8 8 1574 35 0 6 12 261 3
2 2 8 540 9 4 4 10 1595 43 4 8 10 251 3
1 5 7 191 3 0 6 10 2002 0 2 6 12 593 7
2 6 6 164 3 6 6 8 1989 25 8 8 8 1962 23
0 4 8 408 7 3 7 9 296 31
3 5 7 1146 13 2 6 10 104 14
c) Structure solution
Given the multiplicities of the available sites and the content of the unit cell, La atoms may be
placed in 8(a) or 8(b) sites. Site symmetry is different in this space group: 8(a) is a point, which is
located on the intersection of 4- and 3-fold axes, while 8(b) site has point symmetry m3. Thus,
placing La atom in 8(a) or 8(b) may result in the different models of the crystal structure.
We will begin with La atom in 8(a). The RF calculated using this atom is 54.5 %. The following
Fourier map results in two electron density maxima with the coordinates:
Peak #2: 0, 0, 1/2, [8(b)] and
Peak #4: 0.114, 0, 0.191 [96(i)]
Both peaks have normal interatomic distances. Recalling that Ge is a minority component, we
assume that these two sites are occupied by Ni only, and after they have been included into phase
calculations, the RF is reduced to 28.4 %. The subsequent Fourier map confirms all three atoms.
The coordinates of the atom in 96(i) site change to x = 0.1159, z = 0.1869, and the next RF lowers
to 24.6 %. The following Fourier map indicates that next strongest peak is only ~1/6 of the Ni
atom, and the model of the crystal structure may be considered complete. What is left to Rietveld
refinement is the exact distribution of Ni and Ge atoms among the corresponding crystallographic
sites.
Even tough it appears that the crystal structure has been solved, it is still may be necessary to test
the second possibility, i.e. La atoms located in the 8(b) sites. When La atoms are placed in 8(b)
sites the RF remains identical to the previous model: 54.5 %. The subsequent Fourier map results
in additional (Ni) atoms in 8(a) with coordinates 1/4, 1/4, 1/4. Phase computation assuming this
distribution of atoms results in RF = 55.7 %, i.e. it has been increased when compared to just a
single La atom placed in the 8(b) site. The following Fourier map confirms both atoms but results
in no new peaks, which may be easily associated with the missing 96 Ni/Ge atoms. Therefore,
we conclude that the first model is correct and it should be completed by employing Rietveld
refinement, which will be done later (Problem 11).
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Considering the first model, the shortest interatomic distances are as follows:
La – Ni(Ge): 3.32 Å
Ni(Ge) – Ni(Ge): 2.36 Å
Thus, the model is reasonable and it is shown in Figure 55.
Figure 55. The model of the crystal structure of LaNi11.4Ge1.6 showing 1/2 of the unit cell along b.
Statistical distribution of Ni and Ge atoms in the corresponding sites has been assumed.
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8. Consider the powder diffraction pattern collected from a ground Hf2Ni3Si4 powder, which is
shown in Figure 56. The pattern has been indexed in the orthorhombic crystal system and the
unit cell dimensions are a = 5.18, b = 13.65 and c = 6.85 Å. An analysis of the systematic
absences indicates that the following groups of reflections have non-zero intensity:
hkl, h + k = 2n;
hk0, h and k = 2n;
h0l, h and l = 2n;
0kl, k = 2n;
h00, h = 2n;
0k0, k = 2n;
00l, l = 2n.
Pycnometric density is 8.8(5) g/cm3. Solve the crystal structure of this material without
using handbooks and/or databases. Powder diffraction data are found in the files
Ch25Pr08_CuKa.xy and Ch25Pr08_CuKa.raw online.
Figure 56. Powder diffraction pattern collected from a ground Hf2Ni3Si4 powder on an HZG-4a
diffractometer. The data were collected with a step 2 = 0.02°. The inset shows splitting of some Bragg
peaks, which requires a relatively large orthorhombic lattice to index this seemingly high-symmetry pattern
(low Bragg angle peaks appear regularly spaced). Data courtesy of Dr. L.G. Akselrud.
Solution:
a) Space group symmetry and unit cell content
The given set of systematic absences results in the two possible space groups symmetry: C2cb or
Cmca (see Table 2.13). From the unit cell volume and mass of the formula unit, we easily
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establish that the number of Hf2Ni3Si4 formula units in the unit cell is 4. The multiplicities of site
positions in both space groups are adequate to locate 8Hf, 12 Ni and 16 Si atoms, and we will
attempt to solve this crystal structure in the centrosymmetric space group Cmca.
b) Individual structure factors
By employing Le Bail’s full pattern decomposition, individual intensities of ~270 Bragg
reflections can be extracted from the powder diffraction pattern. Even though the refinement
presents no real difficulties and slowly converges to low residuals (Rp = 2.59 %, Rwp = 3.49 %, 2
= 1.65 and Rexp = 2.71 %, see Figure 57), multiple and closely overlapped Bragg reflections may
be a problem during structure solution from first principles. Furthermore, it is unrealistic to
expect a low residual during structure solution. Heavy peak overlap is illustrated in Figure 58.
b) Structure solution
A best solution after applying direct methods with all default settings (WinCSD software suite)
results in a single heavy atom with the following coordinates: x = 0, y = 0.1070, z = 0.9115.
These coordinates correspond to an atom in the 8(f) site. The shortest distance between the
symmetrically equivalent atoms is 3.16 Å, which is slightly larger than two atomic radii of Hf (rHf
= 1.55 Å). Calculation of phase angles results in RF = 48.4 % and the subsequently calculated
Fourier map confirms the placement of Hf (first peak with relative height 142) and reveals three
additional electron density maxima:
4(b): x = 0, y = 0, z = 0.5; Height 26 - Assumed Ni
8(e): x = 0.25, y = 0.219, z = 0.25; Height 23 - Assumed Ni
8(e): x = 0.25, y = 0.053, z = 0.25; Height 17 - Assumed Si
with all distances within normal limits. The fifth peak has height 13 but it is located too close to
Hf and therefore, is considered as a false peak. Proceeding as indicated above, after including
three additional independent atoms into calculation of phases, RF lowers to 41.0 %. The
corresponding Fourier map confirms four atoms located in the unit cell so far. The first four
strongest electron density peaks correspond to Hf, two Ni and one Si atoms. There is no sharp
reduction in peak height, and peaks No. 5 and 6 are false maxima (the distances are abnormally
short). However, peak No. 7, which has coordinates
8(f): x = 0, y = 0.1746, z = 0.5031; Height 7 - Assumed Si
fits into the structure quite well. Assuming this is the missing silicon atom, the subsequent phase
computation yields RF = 40.1 % - a minimal reduction, but at least not an increase. The next
Fourier map confirms all five independent atoms, which are now first five strongest peaks. There
is still no sharp reduction of peak height after the last real atom, which can be explained by
inaccuracies in the individual structure factors (see Figure 7). All interatomic distances are
normal. The content of the unit cell matches alloy stoichiometry and the number of formula units
established from the gravimetric density of the material.
Thus, the final model of the crystal structure is listed in Table 22 and it is visualized in Figure 59.
The structure makes both physical and chemical sense and the solution should be completed by
Rietveld refinement (see Problem 12).
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Figure 57. Observed (pluses) and calculated (red line) powder diffraction patterns of Hf2Ni3Si4 after the
completion of Le Bail’s full pattern decomposition. The green line represents the difference between the
observed and calculated patterns and the blue bars indicate calculated positions of both K1 and K2
components of Bragg reflections.
Figure 58. A fragment of the powder diffraction pattern of Hf2Ni3Si4 after the completion of Le
Bail’s full pattern decomposition highlighting heavy overlapping of Bragg peaks.
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Table 22. Coordinates of atoms in the model of the crystal structure of Hf2Ni3Si4 determined from
first principles.
Atom Site x y z
Hf 8(f) 0 0.1070 0.9115
Ni1 4(b) 0 0 1/2
Ni2 8(e) 1/4 0.219 1/4
Si1 8(e) 1/4 0.053 1/4
Si2 8(f) 0 0.1746 0.5031
Figure 59. The model of the crystal structure of Hf2Ni3Si4.
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9. The compound VO(CH3COO)2 crystallizes in the orthorhombic crystal system with a =
14.066, b = 6.878, c = 6.925 Å. Its gravimetric density is less than 2 g/cm3. The powder
diffraction pattern (data files Ch25Pr09_CuKa.xy and Ch25Pr09_CuKa.raw) is shown in
Figure 60. The extracted structure amplitudes (data file Ch25Pr09_CuKa.hkl) are also
found online. Solve the crystal structure of this material.
Figure 60. Powder diffraction pattern collected from a VO(CH3COO)2 powder on a Scintag XDS2000
diffractometer. The data were collected with a step 2 = 0.02°. The strongest peak is shown at ~¼ of its
intensity.
Solution:
Analysis of the systematic absences (the file with extracted intensities may be analyzed directly)
results in the following possible space groups symmetry: Cmcm, Cmc21, and C2cm (Ama2 in the
standard setting). From the approximate gravimetric density, we find that there are four formula
units in the unit cell, i.e. we are looking for 4V, 12O, 8C and 16H atoms in the unit cell (finding
the latter is impossible using extracted intensities). Thus, when V and perhaps some other atoms
occupy special positions, the centrosymmetric group Cmcm can be employed. However, multiple
attempts to solve the structure in this space group failed as no reasonable model has been found.
Next, non-centrosymmetric group was tried starting from Cmc21 as a more common group for
inorganic compounds than C2cm.
SHELXS direct methods with the default Emin=1.2 result in 1 independent V and 3 independent O
atoms (all of them were assigned V type but both the distances and chemical composition indicate
that only the first peak should be V). SHELX refinement results in RF = 28% and the difference
Fourier map yields two strong peaks: the first bonds two oxygen atoms (O2 and O3) together and
the second peak is bonded to the first peak. This configuration is nothing else as four non-
hydrogen atoms in the acetate anion:
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O
CH3 C
O
After checking bond angles (which are close to the expected for the geometry of the anion), both
peaks can be added as C-atoms. The final refinement using extracted intensities and SHELX
converges to RF = 15%. This model of the crystal structure is listed in Table 23 and illustrated in
Figure 61.
Table 23. Coordinates of non-hydrogen atoms in the crystal structure of VO(CH3COO)2 solved using direct
phase determination techniques and Fourier calculations from powder diffraction data.
Atom x y z Site Uiso V1* C1 C2
V1 0.0000 -0.0250 0.0955 4(a) 0.056
O1 0.0000 0.1260 -0.2022 4(a) 0.053 1.56, 2.31
O2 0.0989 0.1796 0.1319 8(b) 0.061 2.00 1.26
O3 -0.0982 -0.1844 -0.0448 8(b) 0.051 2.01 1.18
C1 -0.1247 -0.2280 -0.2007 8(b) 0.043 1.63
C2 -0.2015 -0.4058 -0.2142 8(b) 0.057 1.63
*
The last three columns contain the distances to the indicated atom. Errors in distances are around 0.05 Å.
Figure 61. Locations of non-hydrogen atoms in the model of the crystal structure of VO(CH3COO)2.
Vanadium atoms (red) are located in the centers of the octahedra formed by oxygen atoms.
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10. Complete structure determination and perform Rietveld refinement of the model of SrSi2,
which you solved in Problem 6. The experimental powder diffraction pattern is located
online in the file Ch25Pr10_CuKa.raw.
Solution:
Rietveld refinement, beginning from profile parameters determined during Le Bail’s full patter
decomposition and coordinates of atoms as established during the solution of Problem 6 from this
Chapter, easily converges to Rp = 6.34 %, Rwp = 8.55 %, RB = 2.65 %, and 2 = 2.11. Parameters
of individual atoms have been refined in anisotropic approximation and these are listed in Table
24. Screen image of the corresponding Rietveld plot, produced by LHPM-Rietica, is shown in
Figure 62. The drawing of the crystal structure, including displacement ellipsoids, is shown in
Figure 63. All interatomic distances remain normal and thermal ellipsoids are physical.
Figure 62. The observed (pluses) and calculated (red line) powder diffraction patterns of SrSi2. The
difference is shown using the green line and the blue-colored vertical tick-marks indicate calculated
positions of both K1 and K2 components of Bragg reflections.
Table 24. Atomic parametersa determined from Rietveld refinement of SrSi2.
Atom Site x y z 11 12
Sr 4(a) 3/8 3/8 3/8 57(1) 8(1)
Si 8(c) 0.0776(1) 0.0776(1) 0.0776(1) 44(1) 3(1)
a
Anisotropic displacement parameters in both sites are constrained by symmetry: 11 = 22 = 33, and
12 = 13 = 23.
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Figure 63. The fully refined model of the crystal structure of SrSi2.
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Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
11. Complete the solution of the crystal structure and perform Rietveld refinement of the model
of LaNi11.4Ge1.6 from Problem 7. The experimental powder diffraction pattern is located
online in the file Ch25Pr11_CuKa.raw.
Solution:
Starting from profile parameters determined during Le Bail’s refinement and from the model of
the crystal structure determined during the solution of Problem 7 in this Chapter, Rietveld
refinement converges to Rp = 6.47 %, Rwp = 8.16 %, RB = 3.73 %, and 2 = 1.07, assuming
statistical distribution of Ni and Ge atoms in 8(b) and 96(i) sites. Refinement of the population
parameters of Ni and Ge, while keeping overall isotropic displacement parameter approximation,
indicates that 8(b) sites are occupied by pure Ni, while 96(i) sites are occupied by both Ni and Ge.
Rietveld refinement is easily completed in the anisotropic approximation and it converges to Rp =
6.40 %, Rwp = 8.08 %, RB = 3.39 %, and 2 = 1.05. The fully refined individual atomic parameters
are listed in Table 25 and Table 26, and the model of the crystal structure is shown in Figure 64.
The screen image of the corresponding Rietveld plot produced by LHPM-Rietica is shown in
Figure 65.
The chemical composition of the material, as refined from the powder diffraction data (Table 25),
is LaNi11.3(1)Ge1.7(1), which is nearly an ideal match with the nominal alloy stoichiometry.
Table 25. Atomic parameters determined from Rietveld refinement of LaNi11.4Ge1.6.
Atom Site x y z g (%)
La 8(a) 1/4 1/4 1/4 100
Ni 8(b) 0 0 1/2 100
Ni2 96(i) 0.1173(1) 0 0.1794(1) 85.8(1)
Ge2 96(i) 0.1173(1) 0 0.1794(1) 14.2(1)
Table 26. Anisotropic displacement parametersa determined from Rietveld refinement of LaNi11.4Ge1.6.
Atom Site 11 22 33 13
La 8(a) 13(1) 13(1) 13(1) 0
Ni 8(b) 18(1) 18(1) 18(1) 0
Ni2 96(i) 13(1) 18(1) 13(1) 2(1)
Ge2 96(i) 13(1) 18(1) 13(1) 2(1)
a
Anisotropic displacement parameters in all sites are constrained by symmetry as follows: 8(a) and 8(b),
11 = 22 = 33, and 12 = 13 = 23 = 0; 96(i), 12 = 23 = 0.
Copyright © 2009 by Springer 134
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Figure 64. The fully refined model of the crystal structure of LaNi11.4Ge1.6.
Figure 65. The observed (pluses) and calculated (red line) powder diffraction patterns of LaNi11.4Ge1.6. The
difference is shown using the green line and the blue-colored vertical tick-marks indicate calculated
positions of both K1 and K2 components of Bragg reflections.
Copyright © 2009 by Springer 135
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
12. Complete the solution of the crystal structure and perform Rietveld refinement of the model
of Hf2Ni3Si4 from Problem 8. The experimental powder diffraction pattern is located online
in the file Ch25Pr12_CuKa.raw.
Solution:
Rietveld refinement beginning from profile parameters determined during Le Bail’s full pattern
decomposition and the model of the crystal structure established during the solution of Problem 8
converges to the following residuals: Rp = 3.36 %, Rwp = 4.36 %, RB = 2.33 %, and 2 = 2.58.
The structure has been refined with individual isotropic displacement parameters and with a
preferred orientation correction along the [100] direction, as shown in Table 27. Refinement of
anisotropic displacement parameters yields unphysical results. All distances remain normal and
the plot of the observed and calculated intensities is shown in Figure 66.
Figure 66. The observed (pluses) and calculated (red line) powder diffraction patterns of Hf2Ni3Si4. The
difference is shown using the green line and the blue-colored vertical tick-marks indicate calculated
positions of both K1 and K2 components of Bragg reflections.
Table 27. Atomic parameters determined from Rietveld refinement of Hf2Ni3Si4. Space group Cmca, a =
5.18060(7), b = 13.6582(2), c = 6.85621(8) Å.
Atom Site x y z B (Å2)
Hf 8(f) 0 0.1047(1) 0.9029(1) 0.79(2)
Ni1 4(b) 0 0 1/2 1.1(1)
Ni2 8(e) 1/4 0.2283(2) 1/4 1.4(1)
Si1 8(e) 1/4 0.0642(3) 1/4 0.5(1)
Si2 8(f) 0 0.1858(4) 0.5188(6) 1.3(1)
Copyright © 2009 by Springer 136
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
The displacement parameters of Ni2 and Si1 possibly indicate some mixing of Si and Ni atoms in
these two sites. However, constrained Rietveld refinement (to maintain the Hf2Ni3Si4
stoichiometry) does not result in the meaningful changes of occupancies (they remain below 2%
and are within experimental errors, even though the displacement parameters of the two atoms
become closer to one another).
Copyright © 2009 by Springer 137
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
13. Perform Rietveld refinement of the hexamethylenetetramine, C6H12N4, using the model
established in Problem 5. The experimental powder diffraction pattern is located online in
the file Ch25Pr13_CuKa.raw.
Solution:
The initial model of the hexamethylenetetramine (HMTA) was taken from the solution of
Problem 5, and it was refined using GSAS. Attempts to refine anisotropic atomic displacement
parameters for C and N atoms and/or adding and refining H atoms (in the CH2 groups) result in
no improvement but yield unphysical parameters of the structure (open displacement ellipsoids
and incorrect C-H distances). No preferred orientation has been detected. The refinement results
are listed in Table 28 and Table 29 and profile fit is illustrated in Figure 67. Bond lengths and
bond angles (Table 29) are within 5 - 10 standard deviations from those obtained from single
crystal neutron diffraction data,1 which is a good match.
15 25 35 45 55 65 75 85
Figure 67. The observed (blue circles), calculated (red line) and difference (green line) plots of HMTA. The
vertical bars indicate calculated positions of the K1 components of Bragg reflections.
Table 28. The results of Rietveld refinement of HMTA employing GSAS and all available data.
Formula C6H12N4 1.348 g/cm3
Space group I43m Preferred orientation None
A 7.017(2) Å Rp 10.61%
1
M. Terpstra, B.M. Craven, and R.F. Stewart, Hexamethylenetetramine at 298 K: New refinements,
Acta Cryst. A49, 685 (1993)
Copyright © 2009 by Springer 138
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Formula C6H12N4 1.348 g/cm3
V 345.49 Å3 Rwp 15.24%
Z 2 Rexp 2.48%
Formula mass 140.19 a.m.u. RF2 15.34%
Table 29. Atomic parameters and selected geometric characteristics for HMTA obtained using all available
data employing GSAS.
Atom x y z U, Å2 Site
C1 0.2477(9) 0 0 0.050(2) 12(e)
N1 0.1202(4) 0.1202(4) 0.1202(4) 0.050(2) 8(c)
Distances, Å Angles,
C1-N1 1.491(3) N1-C1-N1 106.3(7)
C1-N1-C1 111.0(3)
A very strong Bragg reflection at 2 17.5o may have a deleterious effect on the outcome of
Rietveld refinement (see Chapters 21 and 22). Thus, we will also try to refine this crystal
structure using LHPM-Rietica after excluding this single Bragg reflection from the consideration.
The least squares minimization converges to low residuals and it is possible to refine anisotropic
displacement parameters of both carbon and nitrogen atoms. The hydrogen atom has been added
with the coordinates determined from single crystal data (see the footnote on the previous page).
The results of this refinement are presented in Figure 68 and Table 30 and Table 31.
Table 30. The results of Rietveld refinement of HMTA employing LHPM-Rietica and truncated set of data.
Formula C6H12N4 1.331 g/cm3
Space group I43m Preferred orientationa None
a 7.0443(3) Å Rp 6.84%
V 349.55 Å3 Rwp 9.06%
Z 2 Rexp 3.24%
Formula mass 140.19 a.m.u. RB 2.28%
a
A primary extinction correction was included in the least squares fit.
Table 31. Atomic parameters and selected geometric characteristics for HMTA obtained using truncated set
of data employing LHPM-Rietica.
Atom x y z B, Å2 Site
C1 0.2432(5) 0 0 3.22 12(e)
N1 0.1185(3) 0.1185(3) 0.1185(3) 2.82 8(c)
H1 0.3229 -0.0894 0.0894 16(2) 24(g)
Atom 103U11 3
10 U22 3
10 U33 3
10 U12 103U13 103U23
C1 21(1) 51(2) 51(2) 0 0 7(2)
N1 36(1) 36(1) 36(1) 3(2) 3(2) 3(2)
Distances, Å Angles,
C1-N1 1.471(3) N1-C1-N1 106.7(3)
C1-N1-C1 110.8(1)
Copyright © 2009 by Springer 139
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Figure 68. The observed (pluses), calculated (red line) and difference (green line) plots of HMTA. The
vertical bars indicate calculated positions of the K1 and K2 components of Bragg reflections.
Copyright © 2009 by Springer 140
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
14. Complete the solution of the crystal structure and perform Rietveld refinement of the model
of vanadyl acetate, VO(CH3COO)2, using the model established in problem 9. The
experimental powder diffraction pattern is located online in the file Ch25Pr14_CuKa.raw.
Solution:
The starting model was taken from the solution of Problem 9 and refined using GSAS. Attempts
to refine anisotropic displacement parameters for V, O and C atoms and/or adding and refining H
atoms (in the CH3 group) yield no improvement and give unphysical parameters of the structure
(open displacement ellipsoids and incorrect C-H distances). Significant preferred orientation
occurs along two axes due to the one-dimensional framework (see Figure 61 in the solution of
Problem 9). The refinement results are listed in Table 32 and Table 33, and profile fit is
illustrated in Figure 69. Geometry of the structure is quite reasonable, e.g. the sum of C-C-O and
O-C-C angles (Table 33) for the flat acetate ion is 359.
Table 32. The results of Rietveld refinement of VO(CH3COO)2
Formula VO(CH3COO)2 1.835 g/cm3
Space group Cmc21 Preferred orientation [001] 1.584
a 14.0652(6) Å [010] 0.849
b 6.8777(3) Å PO correction (min,max) 0.517, 1.816
c 6.9236(5) Å Rp 7.20%
V 669.75 Å3 Rwp 9.97%
Z 4 Rexp 1.90%
Formula mass 185.03 a.m.u. RF2 11.21%
Table 33. Atomic parameters and selected geometric characteristics for VO(CH3COO)2
Atom x y z U, Å2 Site
V1 1/2 0.4711(5) 0.583(2) 0.009(1) 4(a)
O2 1/2 0.615(2) 0.294(3) 0.012(2) 4(a)
O3 0.5989(8) 0.681(1) 0.647(2) 0.012(2) 8(b)
O4 0.4054(9) 0.322(1) 0.463(2) 0.012(2) 8(b)
C1 0.3644(9) 0.282(2) 0.297(3) 0.012(2) 8(b)
C2 0.3101(8) 0.085(2) 0.281(3) 0.012(2) 8(b)
Distances, Å Angles,
C1-O3 1.19(3) O3-C1-O4 122.0(14)
C1-O4 1.31(3) O3-C1-C2 109.6(20)
C1-C2 1.56(2) O4-C1-C2 117.4(17)
V1-O2 2.24(2)
V1-O2 1.58(2)
V1-O3 2.05(1) 2
V1-O4 1.88(1) 2
Copyright © 2009 by Springer 141
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
10 20 30 40 50 60 70 80 90
Figure 69. The observed (blue circles), calculated (red line) and difference (green line) plots of
VO(CH3COO)2. The vertical bars indicate calculated positions of the K1 components of Bragg reflections.
Copyright © 2009 by Springer 142
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
15. Complete the solution of the crystal structure and perform Rietveld refinement of the model
of manganese oxide, MnO2, which crystallizes in the space group P42/mnm with a = 4.41, c
= 2.88 Å. The gravimetric density of the material is = 5.10 g/cm3. Assume that manganese
atoms occupy the site 2(a): 0,0,0. The experimental powder diffraction pattern is found
online in the file Ch25Pr15_CuKa.raw.
Solution:
A single Mn atom in the origin (0,0,0) was used as the initial model. All profile parameters and
isotropic displacement parameter of Mn were refined using GSAS. The only oxygen atom can be
easily located from a difference Fourier map. Insignificant yet noticeable preferred orientation
along the [001] axis (a typical direction for the tetragonal crystal system) is present. The crystal
structure has chemical composition MnO2 and belongs to the rutile-type (Figure 70). The
refinement results are listed in Table 34 and Table 35 and profile fit is illustrated in Figure 71.
Table 34. The results of Rietveld refinement of MnO2
Formula MnO2 5.168 g/cm3
space group P42/mnm Preferred orientation [001]; 1.032
a 4.40621(6) Å PO correction (min,max) 0.909, 1.049
c 2.87804(5) Å Rp 11.75%
V 55.88 Å3 Rwp 17.34%
Z 2 Rexp 10.38%
Formula mass 86.94 a.m.u. RF2 8.00%
Figure 70. Crystal structure of MnO2 shown along the Z-axis. The blue MnO6 octahedra share
edges (along the Z-axis) and corners (in the XY-plane) to form a three-dimensional framework.
Copyright © 2009 by Springer 143
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Table 35. Atomic parameters and selected bond lengths (Å) for MnO2
Atom x y z U, Å2 Site
Mn 0 0 0 0.0070(3) 2(a)
O 0.3051(4) 0.3051(4) 0 0.0169(8) 4(f)
Distances, Å
Mn-O 1.901(3) 2
Mn-O 1.883(2) 4
20 30 40 50 60 70 80 90 100 110
Figure 71. The observed (blue circles), calculated (red line) and difference (green line) plots of MnO2. The
vertical bars indicate calculated positions of the K1 components of Bragg reflections.
Copyright © 2009 by Springer 144
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
16. Solve the crystal structure and perform Rietveld refinement of the model of NaV2O5, which
crystallizes in the space group Pmmn with a = 11.317, b = 3.611, c = 4.807 Å. It is known
that V2O5 belongs to the same space group symmetry with the unit cell dimensions a = 11.51,
b = 3.564, c = 4.368 Å. The coordinates of atoms in V2O5 are: V in 4(f): 0.10, ¼, 0.90; O1
in 4(f): 0.10, ¼, 0.53; O2 in 4(f): -0.07, ¼, ~0.00; O3 in 2(a): ¼, ¼,~0.00. The experimental
powder diffraction pattern is found online in the file Ch25Pr16_CuKa.raw.
Solution:
The initial model (the vanadium oxide framework) was adopted from the V2O5 structure, which
has the same symmetry and similar lattice parameters. It was refined using GSAS. Sodium atom
can be found as the strongest peak on a difference Fourier map. Noticeable preferred orientation
along the [001] axis is due to the layered structure shown in Figure 72. Final results are provided
in Table 36 and Table 37 and profile fit is illustrated in Figure 73.
Table 36. The results of Rietveld refinement of NaV2O5
Formula NaV2O5 3.461 g/cm3
Space group Pmmn Preferred orientation [001], 0.894
a 11.3202(2) Å PO correction (min,max) 0.845, 1.401
b 3.61231(6) Å Rp 8.76%
c 4.80766(10) Å Rwp 11.35%
V 196.60 Å3 Rexp 6.23%
Z 2 RF2 5.52%
Formula mass 204.87 a.m.u.
Figure 72. Crystal structure of NaV2O5 shown along the X-axis. Pink VO5 square pyramids share edges and
form double chains along the Y-axis, which in turn share corners (along the X-axis) and form a layer. Na
atoms (light-blue spheres) occupy tetragonal antiprismatic cavities between the layers.
Copyright © 2009 by Springer 145
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Table 37. Atomic parameters and selected bond lengths (Å) for NaV2O5
Atom x y z U, Å2 Site
V1 0.0975(1) 1/4 0.8923(2) 0.0125(5) 4(f)
O1 0.1153(3) 1/4 0.5604(7) 0.0104(8) 4(f)
O2 -0.0745(3) 1/4 -0.0066(7) 0.0104(8) 4(f)
O3 1/4 1/4 0.0223(10) 0.0104(8) 2(a)
Na 3/4 1/4 0.6410(7) 0.019(2) 2(b)
Distances, Å
V1-O1 1.608(3) Na-O1 2.555(3) 4
V1-O2 2.007(4) Na-O2 2.611(4) 2
V1-O2 1.906(1) 2 Na-O3 2.425(4) 2
V1-O3 1.836(2)
10 20 30 40 50 60 70 80 90
Figure 73. The observed (blue circles), calculated (red line) and difference (green line) plots of NaV2O5.
The vertical bars indicate calculated positions of the K1 components of Bragg reflections.
Copyright © 2009 by Springer 146
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
17. Complete the solution of the crystal structure and perform Rietveld refinement of the model
of tungsten oxide peroxide hydrate, WO2(O2)(H2O), which crystallizes in the space group
symmetry P21/n with a = 12.07, b = 3.865, c = 7.36 Å, = 102.9º. The location of W has
been found from a Patterson map and it has the coordinates x = 0.680, y = 0.066, z = 0.364.
Note that W usually exhibits octahedral or square-pyramidal coordination (with the peroxide
group, O-O, counted as one ligand). The experimental powder diffraction pattern is found
online in the file Ch25Pr17_CuKa.raw.
Solution:
A single W atom, which may be easily located from a Patterson map, was used as the initial
model of the crystal structure. The latter was refined using GSAS. Positions of O-atoms were
recovered from two sequential difference Fourier maps as follows: the first four O-atoms were
located; several cycles of Rietveld refinement were performed with W and O-atoms; one missing
O-atom was identified from the second Fourier map. Preferred orientation along [010] axes is
unusually low for this type of a one-dimensional framework, shown in Figure 74 where one can
see the chains of edge sharing octahedra with one corner occupied by peroxo-group (O3-O4) and
one by water molecule (O5). The results of refinement are listed in Table 38 and Table 39 and
profile fit is illustrated in Figure 75.
Figure 74. The crystal structure of WO2(O2)(H2O) shown along the X-axis. The W-atom coordination
polyhedron (purple) includes 4 single O atoms, a water molecule, and one peroxo-group (O2). The latter is
counted as one ligand, thus yielding octahedra, which share edges along the Y-axis forming double-chains
bound together by hydrogen bonds (the latter are not shown).
Table 38. The results of Rietveld refinement of WO2(O2)(H2O)
Formula WO2(O2)(H2O) Formula mass 265.86 a.m.u.
Space group P21/n 5.279 g·cm-3
a 12.0697(6) Å Preferred orientation [010], 0.982
b 3.8637(2) Å PO correction (min,max) 0.973, 1.056
c 7.3587(4) Å Rp 5.46%
Copyright © 2009 by Springer 147
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
Formula WO2(O2)(H2O) Formula mass 265.86 a.m.u.
102.909(3) Rwp 6.86%
V 334.49 Å3 Rexp 2.57%
Z 4 RF2 5.75%
Table 39. Atomic parameters and selected bond lengths (Å) for WO2(O2)(H2O)
Atom x y z U, Å2 Site
W 0.6783(2) 0.0682(5) 0.3645(3) 0.026(1) 4(e)
O1 0.5552(15) 0.073(5) 0.208(2) 0.004(3) 4(e)
O2 0.2049(14) -0.069(6) 0.826(3) 0.004(3) 4(e)
O3 0.3582(16) 0.120(6) 0.413(3) 0.004(3) 4(e)
O5 0.1369(13) -0.040(5) 0.425(2) 0.004(3) 4(e)
O4 0.1342(16) 0.264(5) 0.092(4) 0.004(3) 4(e)
Distances, Å
W-O1 1.66(2) W-O3 1.93(2)
W-O2 2.20(2) W-O4 1.98(2)
W-O2 1.99(2) W-O5 2.42(2)
W-O2 1.99(2)
O3-O4 1.38(2)
10 20 30 40 50 60 70
Figure 75. The observed (blue circles), calculated (red line) and difference (green line) plots of
WO2(O2)(H2O). The vertical bars indicate calculated positions of the K1 components of Bragg reflections.
Copyright © 2009 by Springer 148
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
18. Locate the missing water molecule and perform Rietveld refinement of zinc vanadate
(Zn3(OH)2V2O7·2H2O), which crystallizes in the space group Pm1 with a = 6.05, c = 7.19 Å
starting from the following model: Zn in 3(e): ½,0,0; V in 2(c): 0, 0, z, z = 0.25, O1 in 2(d):
⅔, ⅓, z, z = 0.88; O2 in 6(i): x, 2x, z, x = 0.15, z = 0.82; O3 in 1(b): 0, 0, ½. The
experimental powder diffraction pattern is found online in the file Ch25Pr18_CuKa.raw.
The data have been affected by a considerable sample displacement error: ~0.2 mm for a 250
mm goniometer radius.
Solution:
The initial model included positions of metals and oxygen atoms of the framework and was
refined using GSAS. Coordinates of the oxygen atom from a water molecule, residing in the large
cavity, could be recovered from a difference Fourier map and refined. However, the water
molecule appears to be displaced both from the center of the cavity (2/3,1/3,1/2) and from the
three-fold axis (2/3,1/3,z). Therefore, it was refined with the population factor 1/3. A significant
preferred orientation effect along the [001] axes (a typical direction for the hexagonal crystal
system) was detected. The value of the preferred orientation parameter (0.903) is lower than 1,
which agrees with the layered framework depicted in Figure 76. The refinement results are listed
in Table 40 and Table 41, and profile fit is illustrated in Figure 77. This structure, solved from
powder diffraction data, is on the cover of 12th issue of volume 53C, of Acta Crystallographica.
The corresponding CIF file may be used as an example of submitting Rietveld refinement data
(ftp://ftp.iucr.org/pub/rietxmpl.cif).
Table 40. The results of Rietveld refinement of Zn3(OH)2V2O7·2H2O
Formula Zn3(OH)2V2O7·2H2O 3.490 g/cm3
Space group P3m1 Preferred orientation [001], 0.903
a 6.05341(8) Å PO correction (min,max) 0.857, 1.360
c 7.1969(1) Å Rp 7.03%
V 228.39 Å3 Rwp 9.82%
Z 1 Rexp 1.74%
Formula mass 480.06 a.m.u. RF2 6.71%
Table 41. Atomic parameters and selected bond lengths (Å) for Zn3(OH)2V2O7·2H2O
Atom x y z U, Å2 Site
Zn 1/2 0 0 0.0277(7) 3(e)
V 0 0 0.2518(3) 0.0161(8) 2(c)
O1 2/3 1/3 0.8812(12) 0.025(2) 2(d)
O2 0.1541(5) 0.3082(10) 0.8258(6) 0.025(2) 6(i)
O3 0 0 1/2 0.025(2) 1(b)
O4w* 0.6032(30) 0.3016(15) 0.480(3) 0.025(2) 6(i)
Distances, Å
Zn-O1 1.945(4) 2 V-O2 1.709(5) 3
Zn-O2 2.208(3) 4 V-O3 1.787(2)
*
Occupation factor of water is 1/3 as it is disordered around an ideal position (center of inversion at
2/3,1/3,1/2).
Copyright © 2009 by Springer 149
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
a)
b)
Figure 76. Zn3O8 layer (a) is built from close-packed O atoms with 3/4 octahedra (blue) occupied by Zn
atoms. Pyrovanadate V2O7 groups act as pillars between the layers (b), resulting in large cavities filled with
the water molecules (green spheres). The latter is shown fully ordered for clarity.
Copyright © 2009 by Springer 150
Fundamentals of Powder Diffraction and Structural Characterization of Materials. Second Edition.
10 20 30 40 50 60 70 80 90 100 110 120
Figure 77. The observed (blue circles), calculated (red line) and difference (green line) plots of
Zn3(OH)2V2O7·2H2O. The vertical bars indicate calculated positions of the K1 components of Bragg
reflections.
Copyright © 2009 by Springer 151
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