CHAPTER ONE

CRYSTAL STRUCTURE
Introduction
For long / centuries matter in solid state was a subject of enormous fascination mainly because of
two attributes: utility and beauty, which still are just as important in physics today.
Industrial applications have made solid-state physics, or condensed-matter physics, the largest
subfield of physics, as evidenced by the number of pages allocated in physics journals and the
number of physicists employed in this field.
The beautiful symmetry and regularity of crystalline solids have both allowed and stimulated
rapid progress in the physics of crystalline solids in the 20th century. Interestingly, although rapid
theoretical progress has occurred with the most random (gases) and the most regular (crystalline
solids) atomic arrangements, much less has been done with liquids and amorphous (irregular)
solids until quite recently. Applications such as solar cells, memory elements, fiber-optic
waveguides, and xerography have driven the relatively recent rush of interest in low-cost
amorphous materials.

What is a crystal?
A crystal is formed by adding atoms in a constant environment, usually in a solution. This reminds
of possibly the first crystal ever known; a natural quartz crystal grown in a slow geological process
from a silicate solution in hot water under pressure. The crystal form develops as identical building
blocks are added continuously. The building blocks here are atoms or groups of atoms. The crystal
thus formed is a three-dimensional periodic array of identical building blocks, apart from any
imperfections and impurities that may accidentally be included or built into the structure.
A crystalline solid therefore, consists of a large number of atoms arranged in a regular array,
forming a periodic structure. The bonding schemes for molecules are also appropriate for
describing the bonding mechanisms in solids. For example, the ions in the NaCl crystal are
ionically bonded, while the carbon atoms in the diamond structure form covalent bonds. Another
type of bonding mechanism is the metallic bond, which is responsible for the cohesion of copper,
silver, sodium, and other metals. Finally, the weakest type of bonding, van der Waals bonding, is
responsible for the cohesion of organic solids and rare gas crystals.

Two-Dimensional Lattices
 A crystal is a solid where the atoms are arranged in the form of a lattice. A lattice is an
arrangement of points where the same pattern repeats over and over again.
 If one were to move from place to place over a lattice taking photographs it would be
impossible to tell one part of the lattice from another. Two-dimensional lattices are much
easier to picture and understand than their three-dimensional counterparts.
 Lattice points are periodic points in space: fig 1

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 Fig. 1: lattice points is space

 a1 and a2 are the lattice vectors. Every lattice point can be located as
rmn= m a1 + n a2 (m, n are integers)
or in three dimensional case:
rlmn= l a1 + m a2 + n a3 (l, m, n are integers)
 Two points, r and r’ related by translational vector
r’ = r + l a1 + m a2 + n a3 (l, m, n are integers) are equivalent
environmentally.
Note: the lattice vectors are properties of the materials.

Bravais lattice
 This is the simplest type of lattice. In a Bravais lattice the neighborhood of each and every
point is exactly the same as the neighborhood of every other point. In two dimensions, the
location of every point in such a lattice can be described in the form,

r = m a1 + n a2 (m, n are integers)

where the two-dimensional vectors a1 and a2 are called primitive vectors and must be linearly
independent (not all in the same plane).
 The vectors are said to span or generate the lattice. Thus ∑ 𝑛𝑖 𝑎𝑖 is reached by moving 𝒏𝒊
step of length 𝑎𝑖 in the direction of 𝒂𝒊 for i = 1, 2 and 3.

Fig. 2: showing apportion of a 2-D Bravais lattice

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  Consider the figure 2 above, showing a 2-D Bravais lattice of no particular symmetry: the
oblique net. Primitive vectors 𝒂𝟏 and 𝒂𝟐 are shown. All points in the net are linear
combinations of these with integral coefficients; for example, P = a1 + 2a2, and Q = -a1 +
a2.

Two-Dimensional Lattice Types

 There are four distinct types of restriction, and each leads to what we may call a special
lattice type. Thus there are five distinct lattice types in two dimensions, the oblique lattice
and the four special lattices shown in Fig. 4. Bravais lattice is the common phrase for a
distinct lattice type; we say that there are five Bravais lattices in two dimensions.

Fig. 4: Four special lattices in two dimensions (kittel, 8th edn. Pg. 8)

 Figure 5 also shows the Wigner-Seitz cells for each Bravais lattice type (Marder, M. P.,
2nd edn. Pg. 9)

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Fig. 5: The five two-dimensional Bravais lattices and their Wigner-Seitz cells for each lattice. Note
that the centered rectangular lattice can be built by repetition of the structure in the hollow
box, which shows how it obtains its name.

 A Wigner-Seitz cell is a primitive cell constructed by the following method:

1. draw lines to connect a given lattice point to all nearby lattice points;
2. at the mid-point and normal to these lines, draw new lines or planes;
3. the smallest volume enclosed by these new lines or planes is the Wigner- Seitz cell.

Primitive and conventional cells

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  Because lattices are created by repeating small basic units over and over throughout space,
the full information of a crystal can be contained in a small region of space. Such a region,
chosen to be as small as it can be, is called a primitive unit cell.
 Primitive cell is the most “economic” way to define a cell. There is no overlap if you
translate a primitive cell with the lattice vectors. For this reason, all primitive cells have
the same volume V: (same area when in 2D)

V= |a1 ⋅ (a2 × a3)|

 A primitive cell contains only one lattice point (unless positioned that there are points on
its surface). It follows that if n is the density of points in the lattice and v is the volume of
the primitive cell, then nv = 1. Thus v =1/n. since this result holds for any primitive cell,
the volume of the a primitive cell is independent of the choice of cell
 If the primitive cell is a parallelepiped with lattice points at each of the eight corners,
each lattice point is shared among eight cells, so that the total number of lattice points in
the cell is one: 8*(1/8) = 1.
 A non-primitive cell (conventional cell) can be considered as a larger primitive cell with a
basis.

Fig. 6: primitive and conventional cell

 The way to define a primitive- or conventional cell are not unique. For example, for the
square lattice, a square can be used as a primitive cell, as shown in Figure 7 (A).

Fig. 7: Two primitive cells for the square lattice: one cell has a particle at the
corner, while the other has a particle at the center.

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  Comparing Figures 7(A) and 7(B) shows that primitive cells are not unique. However all
different choices must have exactly the same area. The reason is that in a Bravais lattice
the primitive cell contains exactly one particle, while the primitive cells put end to end fill
the crystal; the reason why, the volume of the primitive cell is exactly the inverse of the
density of the crystal.
 The choice of primitive vectors is not unique—one makes choices that are as simple as
possible or that have some nice symmetry to them. An example of this arbitrariness of the
choice of the primitive translation vectors is illustrated in the figure below: consider the
2- D rectangular bravais lattice generated by fundamental vectors t1 and t2 given as;

t1 = (a, 0, 0) t2 = (0, b, 0)
the same bravais lattice can be generated for instance by the primitive vectors
t1’ = (2a, -b, 0) t2’ = (-a, b, 0)
the relationship connecting t1’ and t2’ to t1 and t2 is,

The transformation matrix has integer elements and unit determinant.

As shown in figure 8 the choices are perfectly equivalent and the area of the unit cell is invariant;
the choice of primitive vectors t1 and t2 and rectangular primitive unit cell appears preferable,
compared to the oblique parallelogram shaped unit cell given by t1’ and t2’ despite evidently both
being equivalent

Fig. 8. Illustration of a 2D rectangular Bravais lattice.

The lattice can be described by the primitive translation vectors t1 = (a, 0, 0) and t2 = (0, b, 0).
Although this is the most natural choice, infinite other choices are possible, the figure illustrates
the choice t1’ = (2a, -b, 0) and t2’ = (-a, b, 0). Whatever choice is done, the area of the unit cell is
invariant and equals ab

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Example: Hexagonal Lattice.
1. To create primitive cell for a hexagonal lattice, show that taking,
𝑎1 = 𝑎(1 0) a is the lattice spacing
⃗⃗⃗⃗
1 √3
𝑎2 = a ( 2
⃗⃗⃗⃗ )
2

Can as well be equal as choosing,

⃗⃗⃗⃗ 1 √3
𝑎1′ = a (− 2 )
2

⃗⃗⃗⃗ 1 √3
𝑎2′ = a ( 2 )
2

2. a) The hexagonal lattice may be viewed as a special case of the centered rectangular
lattice. Referring to Figure 5 and to the conventional unit cell depicted there, find the
ratio c/a for which the centered rectangular lattice would become hexagonal.
b) Enumerate the symmetries of the hexagonal lattice, and compare them with the
symmetries of the centered rectangular lattice.

 It is possible to describe a bravais lattice with a conventional unit cell as illustrated in figure
9 depicting a 2D bravais lattice known as the centered rectangular lattice.
If we choose as primitive vectors
t1 = (a, 0, 0) and t2 = (a/2, b/2, 0), the primitive unit cell will be a
parallelogram of area ab/2.
 Instead of the primitive cell (which is an oblique parallelogram), it is sometimes preferred
to describe the lattice by conventional unit cell of rectangular shape, double area and
an extra point at the center of the rectangle. Its fundamental vectors are
t1(c) = (a, 0, 0) and t2(c) = (0, b, 0)
the matrix M connecting with t1, t2 with t1(c) , t2(c) is given as;
(𝑐)
𝑡 1 0 𝑡1
( 1(𝑐) ) = ( )( )
𝑡2 −1 2 𝑡2

and has a determinant = 2; the conventional cell defined by t1(c) and t2(c) contains 2
primitive cells

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 Fig. 9: Illustration of the primitive unit cell and conventional unit cell for a 2D centered
rectangular Bravais lattice
N/B
The conventional cell is not the repeating block of smallest volume; thus in the study of the
effects related to the translational symmetry e.g classification of states with wavevector
quantum number, brillouin zone concept, and in general in any problem directly or indirectly
related to the full translational symmetry, we must consider only the primitive translational
vectors and the primitive unit cell. Conventional cells are however of help for a pictorial
description of a number of crystals

Lattice with a basis

 A basis: Defined as a congruent groups of atoms located at each lattice point. e.g.:

In this example, the complete crystal structure will look like:

N/B - Read on Importance of crystal symmetry – Neumann principle: the symmetry

elements of any physical property must include the symmetry elements of the crystal
structure. The physical properties must present a higher, not lower symmetry than the
crystal structure.

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Basis - point groups
 A basis can possess certain symmetry about the lattice point. These symmetric components
are point operation – rotation axis, inversion, mirror (passing through the origin) reflection
etc.
 The symmetry of the basis is specified by the collection of symmetric components forming
a group (point group).
 The point symmetry is restricted because of the translational property of the lattice. The
point symmetry should be compatible with that of the lattice. For example, five-fold
symmetry is not considered because it is not allowed for the lattice.

Three-Dimensional Lattice Types

 In 3 D, symmetry considerations lead to fourteen different Bravais lattices grouped into
seven crystal systems: triclinic, monoclinic (primitive and base- centered), orthorhombic
(primitive, base centered, body centered and face centered), trigonal tetragonal
(primitive, base centered), hexagonal, and cubic (primitive, base centered, body centered
and face centered).
 The classification is based on the equality or inequality;
1. of the lengths a, b, c of the edges of the conventional cell,
2. on the angles α, β, γ between each pair of them, and
3. on possible occurrence of additional lattice points at the center of opposite faces or
at the center of the cell
 The seven crystal systems in order of increasing symmetry (triclinic, monoclinic,
orthorhombic, trigonal, tetragonal, hexagonal, and cubic) and the 14 Bravais lattices as
shown in figure 10.
 Important to note that the symmetry properties are not confined to the translational
invariance, but include in general also appropriate point group operations

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Fig. 10: Classification of the fourteen Bravais lattices into the seven crystal systems. The
conventional parallelepiped cells are shown

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Simple and composite crystals
 A crystal with a single atom in the primitive cell is called a simple crystal (or a simple
lattice); in this case, the basis contains a single vector, which can be taken to be zero (with
appropriate choice of the origin in the crystal). In this crystal lattice, atomic Rn positions
coincide with Bravais translation vectors tn and we have,
Rn =n1t1 + n2t2 +n3t3
 A crystal with two or more atoms (or ions) in the primitive unit cell is called a composite
crystal (or a composite lattice). the equilibrium atomic positions are at the points

Rn 1= d1 + n1t1 + n2t2 +n3t3

Rn 2= d2 + n1t1 + n2t2 +n3t3
……………………………
Rn v= dv + n1t1 + n2t2 +n3t3
 A composite lattice can be thought of as composed by a number of interpenetrating simple
lattices (called sub lattices) equal to the number of vectors of a basis. All the points of a
given sub lattice are related by translation vectors and must thus be occupied by atoms of
the same type; different sub lattices are occupied by atoms of the same or different type

Geometrical description of some crystal structures

 A crystal structure is specified by the knowledge of the primitive translation vectors and
the basis vectors individuating the atomic positions in the unit cell; from this knowledge,
any geometrical property of interest (neighbors, distances and bond lengths, angles, planes,
directions, and also symmetry operations) can easily be worked out.
 An appropriate set of basis vectors d1,, d2, ………….., dv describe the contents of a unit cell.
They specify the atoms or ions in the unit cell by individuating the equilibrium positions
of all the atoms (or ions) in the unit cell

1. Crystal structure of rare gas solids (face – centered cubic lattice)

 The conventional unit cell of the face-centered cubic lattice (fcc) is constructed by putting
atoms on the corners of a cube and then putting an atom on each face, as shown in Figure
11. A set of primitive vectors describing an fcc lattice of spacing a is

t1 = a/2 (0, 1, 1), t2 = a/2 (1, 0, 1), t3 = a/2 (1, 1, 0)

Fig. 11. fcc cubic lattice and the primitive translation vectors t1 , t2, t3 as defined above

 The volume of the primitive cell is,

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 t1. (t2 x t3) =a3/4

this meaning that the primitive cell volume is four times smaller than the volume a3 of the
conventional cubic cell.
 More than twenty of the monoatomic elements adopt the fcc lattice, including copper,
silver, gold, and the noble gases at low temperatures (rare gas solids e.g Ne, Ar. Kr, Xe)

2. Crystal structure of alkali metals (body – centered cubic lattice - bcc)

 The bcc lattice defines the structure of alkali metals - K, Li, Na, Rb, and Cs
 The conventional unit cell of the (bcc) lattice is constructed by putting atoms on the corners
of a cube and then putting an atom in the middle to fill up the big hole in the center, as
shown in Figure 12. A symmetrical set of primitive vectors for a lattice of spacing a is;

t1 = a/2 (-1, 1, 1), t2 = a/2 (1, -1, 1), t3 = a/2 (1, 1, -1)

Fig. 12: the bcc lattice structure

 As in the case of the fcc lattice, the lattice constant a refers to the distance between
corners of the cube, not to the distance between nearest neighbors.
 The volume of the primitive cell is

t1. (t2 x t3) =a3/2. This gives a conventional unit cell twice as large as a primitive
unit cell.
 The atom at origin has 8 nearest neighbors in the positions (a/2)(±1, ±1, ±1) at a distance
(a/2)√3.
 Other elements crystallize (at low temperature) in the monoatomic bcc structure,
including iron, Chromium (Cr – a =2.88 Å), Molybdenum (Mo – a =3.15 Å), Ba (a = 5.03
Å), W (Tungsten – a =3.16 Å) and uranium.

Example
1. Given the bcc crystal, assuming t1, t2, and t3 as the primitive vectors for this structure,
calculate the following;
a. t1 +t2 + t3
b. t2 + t3
c. t1 + t3
d. t1 + t2

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 2. Consider the face-centered and body-centered cubic lattices to be simple cubic lattices
decorated with a basis.
a. Determine the number of basis vectors that is necessary, and write down the basis
vectors for each of these lattices.
b. Determine in each case the ratio of the volume of the conventional unit cell to the
primitive unit cell.

3. The sodium chloride structure – Rocksalt

 The NaCl structure alternates Na+ and Cl- on points of a simple cubic lattice, as shown in
Figure 13. This structure can be described as an fcc lattice of lattice constant a, with a basis
of a sodium atom at (000), and a chlorine atom at a/2(1 0 0).
 Alternatively the structure can be viewed as two interpenetrating fcc lattices displaced by
(a/2)(1, 1, 1) along the body diagonal of the conventional cube; one of the two fcc sub
lattices is composed by cations (Na+) and the other anions (Cl-)
 The primitive translation vectors and the two vectors of the basis of the this crystal system
are given as
t1 = a/2 (0, 1, 1), t2 = a/2 (1, 0, 1), t3 = a/2 (1, 1, 0)
d1 = 0 d2 = a/2 (1, 1, 1)

Fig. 13: the NaCl structure

 Each anion in a given sub lattice has6 nearest neighboring cations (on the other sub lattice)
at a distance a/2, 12 second neighbors of the same type at a distance (a/2)√2 etc.
 Table showing crystals with the NaCl structure

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4. Cesium Chloride
 The cesium Chloride structure (CsCI) alternates cesium and chlorine on the points of a
body-centered cubic lattice, as shown in Figure 14.
 This structure can be described as a simple cubic lattice of lattice constant a, with a basis
of a cesium atom at (000), and a chlorine atom at a/2(l 1 1)

Fig. 14. The CsCl structure can be viewed as a bcc lattice with an
atom of a second type inhabiting the interior of the cube.

 The primitive translation vectors and the two vectors of the basis of the this crystal system
are given as

t1 = a(1, 0, 0) t2 = a(0, 1, 0) t3 = a(0, 0, 1)

d1 = 0 d2 = a/2 (1, 1, 1)
 In this structure, each anion has 8 neighboring cations at distance (a/2)√3; there are 6
second nearest neighbours of the same type at a distance a, etc.
 Table showig crystals with the cesium chloride structure

5. The Diamond Lattice and Zinc blende (Zinc sulfide - ZnS) structure
 The diamond lattice is constructed by taking the fcc lattice and making a copy of it,
displaced relative to the original by (a/4 a/4 a/4). Every atom in the structure has precisely
four nearest neighbors, symmetrically organized around it, at a distance (a/4)√3 as shown
in Figure 15.
 The underlying Bravais lattice is fcc with two carbon atoms forming the basis; the primitive
translation vector and the two vectors of the basis are

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 t1 = a/2 (0, 1, 1), t2 = a/2 (1, 0, 1), t3 = a/2 (1, 1, 0)
d1 = 0 d2 = a/4 (1, 1, 1)

Fig. 15. Crystal structure of Diamond and zinc blende; the end points of the vectors d1 and
d2 of the basis are as indicated. In the diamond structure the two sub lattices are occupied
by atoms of the same type; in the zinc blende structure the two sub lattices are occupied by
different types of atoms

 Only four elements commonly assume the Diamond structure — carbon, silicon,
germanium, and tin — but the cultural status of diamond and technological importance of
silicon and germanium, make this a structure of great significance.
 Among the crystals with the ZnS structure as shown in the table below

Example (Tetrahedral angles)

The angles between the tetrahedral bonds of diamond are the same as the angles between the body
diagonals of a cube. Use elementary vector analysis to find the value of the angle.

6. Hexagonal Close-Packed Structure (hcp)

 Several elements crystallize in the hexagonal close – packed structure (hcp). The structure
can be viewed as follows; consider a 2D array of equilateral triangles (or regular hexagons
including their centers) of edge a, as indicated in the fig. 16. Then one stacks along the z -
axis a second plane of equilateral triangles, above the centers of every other triangle of the
first plane, as indicated in fig. 16. The sequence of planes ABABAB…..AB is then
repeated: the third plane lies directly over the first one, the fourth over the second, and so
on.
 The hcp structure can be pictured as formed by two interpenetrating simple hexagonal
Bravais lattice; the primitive translation vectors and the the two basis vectors are

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 t1 = a(1/2, √3/2, 0), t2 = a(-1/2, √3/2, 0) t3 = c (0, 0, 1)

d1 = 0 d2 = (0, a/√3, c/2)

a) b) c)

Fig. 16: hcp structure; primitive translation vectors and the end points of the basis vectors
are indicated. Fig. 16 b) and c) show the top view of the hcp structure

 The two sub lattices specified by d1 and d2 are occupied by atoms of the same type. In case
where the atoms can be thought of as hard spheres (of radius ro) touching each other, we
have 2ro = a ( contact condition within a hexagonal plane) and also
𝑎2 𝑐2
|𝑑2 | = √( + 4 ) = 2ro (contact condition between 2 adjacent hexagonal planes).
3

The ideal ratio c/a becomes

𝑐 8
= √3 = 1.633;
𝑎
This ratio is only approximately verified in actual hcp crstals.

 More than 25 elements adopt the hcp lattice, including zinc and titanium.

Example
Show that the c/a ratio for an ideal hexagonal close-packed structure (8/3)1/2 =1.633. If c/a
is significantly larger than this value, the crystal structure may be thought of as composed
of planes of closely packed atoms, the planes being loosely stacked.

6. Hexagonal wurtzite structure – Zinc Oxide

 Can be considered as formed by two interpenetrating hcp lattices; in the unit cell there are
four atoms of two different types, forming two molecules (fig. 17). The primitive
translation vectors and basis vectors are

t1 = a(1/2, √3/2, 0), t2 = a(-1/2, √3/2, 0) t3 = c (0, 0, 1)

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 d1 = 0 d2 = (0, 0, uc) d3 = (0, a/√3, c/2) d4 = (0, a/√3, c/2 + uc)

 Both a and c are lattice constants, and u is dimensionles; d1 and d3 are occupied by the
same type of atom, d2 and d4 are occupied by the other type of tom. Each atom is surrounded
by an (almost regular) tetrahedron of atoms of opposite sort; the tetrahedral blocks are
regular if the axis ratio has the ideal value c/a = 1.633 and the parameter u = 3/8 = 0.375.
The adjacent tetrahedral blocks are stacked along the c-axis with the relative orientation
shown in fig. 17 as an example. (Notice that in the cubic zinc blende structure, the adjacent
tetrahedral blocks are stacked along the body diagonal of the conventional cubic cell, and
are rotated by 2π/6 with respect to each other) for ZnO (or zincite) the lattice parameters
are: a = 3.25 Å, c = 5.21 Å, u = 0.345 Å

Fig. 17: hexagonal wurtzite structure. The vectors t1, t2, t3 and d1, d2, d3, d4 as indicated. The
two molecules of the unit cell are encircled for convenience. The orientation of adjacent
tetrahedral surrounding d2 and, d4 are shown

 When u = 3/8 and c/a = √(8/3), every atom is equidistant from four neighbors; although
these extra symmetries are not inevitable for the definition of the structure, natural crystals
display them (see Figure 18 and Table below).

 The table below shows crystals with the wurtzite structure

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Figure 18. The wurtzite (ZnO) structure is an hexagonal structure built with two types of atoms,
and it allows each atom to have four nearest neighbors of the opposite type. It can be
viewed as two interlaced hcp lattices, just as the diamond and zinc blende structures are
built as two interlaced fee lattices (stereo pair)

Lattice Planes (Index System for Crystal/Lattice Planes)

 Lattice planes are flat parallel planes separated by equal distance. All the lattice points lie on
these lattice planes,
 Orientation of the lattice planes is specified by the Miller indices (hkl). The hkl indices are
determined as follows:
1. Find the intercepts on the axes in terms of the lattice constants a1, a2, a3.
The axes may be those of a primitive or non-primitive cell.
2. Take the reciprocals of these numbers.
3. Reduce the numbers to three smallest integers by multiplying the numbers with
the same integral multipliers.
4. The results, enclosed in parenthesis (hkl), are called the Miller indices.

Examples
a. Figure 19 gives indices of important planes in a cubic crystal. It can be seen that the
plane (200) is parallel to (100) and to (100)
b. The plane in figure 20 intercepts the a1, a2, a3 axes at 3a1, 2a2, 2a3.
 The reciprocals of these numbers are 1/3, ½, ½
 The smallest three integers having the same ratio are 2, 3, 3, and
 and thus the indices of the plane are (233)
c. A plane has the following intercepts, 4, 1, 2. Find the miller indices for this plane

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 Fig. 19: Indices of important planes in a cubic crystal. The plane (200)
is parallel to (100) and to (100).

Fig. 20: The plane intercepts the a1, a2, a3 axes at 3a1, 2a2, 2a3

 When speaking of the (200) plane we mean a plane parallel to (100) but cutting the a1 axis at
1/2 a.
 If a plane cuts an axis on the negative side of the origin, the corresponding index is negative,
indicated by placing a minus sign above the index:

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