The structure factor

 The major contribution to the intensity of Bragg reflections are

• The number of electrons in the atoms and

• the extent to which X-rays scattered by various atoms to
reinforce those X-rays.
 Certain diffracted beams have no intensity because the waves scattered
by two different atoms interfere destructively.
 But diffraction from some other hkl planes of these two atoms will
interfere constructively to give reinforced intensity.
 In case of NaCl and KCl crystal structure, for some Bragg reflections
the cations and anions scatter constructively to give appreciable values
to F(hkl)
 while for other Bragg reflections the scattered waves interfere
destructively giving low values for F(hkl) .
 The structure factor

 Figure shows the different behavior of the Bragg reflections with hkl
all odd (the difference of the structure factor)
 And all even (the sum of structure factors)
 The structure factor
 The structure factor is the Fourier transform of the unit cell contents
sampled at reciprocal lattice points, hkl.
 The structure factor amplitude (magnitude) F 

amplitude of the radiation scattered in a particular direction

by the content of one unit cell
F 
amplitude of the radiation scattered
by a single electron at the origin of the unit cell
 F is derived experimentally from the square root of the intensity of
a Bragg reflection.
 The measured structure factor (observed) amplitude are denoted by
F(hkl) o and calculated structure factor for the proposed crystal
structure are designated as F(hkl) c
 The structure factor F has both magnitude F(hkl)  and phase hkl
relative to the origin of the unit cell.
 Theory of Diffraction
A periodic wave can be described by amplitude, wavelength
and relative phase angle.



Amplitude
F

Origin

 Wavelength () = distance between successive maxima in the wave

 Amplitude [F(hkl)] is the height of the crest of the wave.

Fhkl  I
 The relative phase angle  or  (hkl) is the position of the crest of the
wave relative to some origin.
 Theory of Diffraction
 A periodic wave can also be representated by a vector whose
length is proportional to the amplitude and whose
orientation gives a measure of the phase angle.
 We can represent the phase angle on a circle, with 360
representing one wavelength.

 By convention the phase angle is

90
A(hkl)
measured in anti-clockwise directions.
 If the relative phase angle is 0, the
l)
hk

B(hkl)

vector is horizontal, pointing to the

F(

180 (hkl) 0
right.
 If the relative phase angle is 90, the
vector is vertical, pointing upwards.
 Therefore the vector has an angle
270
(hkl) and length F(hkl 
 Theory of Diffraction
 This vector consists of two components: A(hkl), parallel to
the horizontal axis (hkl = 0) and B(hkl), parallel to the vertical axis
(hkl = 90).

 As the wave is periodic, it can be representated as the sum

of cosine and sine waves [amplitude A(hkl) and B(hkl),
respectively].
 The ratio of amplitudes of the two waves gives a measure of
the phase angle.
phase angle tan αhkl B (hkl ) A(hkl )
 The sum of the square of the amplitudes gives the intensity,
which is the square of the amplitude.
2 2 2
intensity  A(hkl )  B(hkl )  F (hkl )
 The structure factor
 The calculation of structure factor amplitude F(hkl)  is broken into two
parts, one A(hkl)  involving cosine function and the other B(hkl)
involving a sine function.

F (hkl )  F (hkl ) e i  hkl

 A(hkl )  iB (hkl )
phase angle hkl tan  1 [ B(hkl) A(hkl)]

the amplitude of the Bragg reflection

F(hkl)  A(hkl)2  B(hkl)2
 Theory of Diffraction
 The meaning of the phase angle in terms of cosine
components of the wave.
Vector diagram

Moving waves

 The intensity at any point is the sum of the square of the

amplitudes of the A and B waves
2 2 2
intensity  A(hkl )  B (hkl )  F (hkl )
 Relative phase angle
 It is the measure of the position of the crest of the waves wrt
crest of the another wave travelling in the same direction, or
the chosen origin of the unit cell (by convention).

 It is the phase of the wave of the hkl Bragg reflection

scattered by the atom in the middle of the unit cell relative
to that of the similar wave travelling in same direction,
scattered by the atom at the origin of the unit cell.
Graphical and algebraic representation of the waves
When a periodic wave travelling in a same direction, they
interfere with each other and the overall effect is the wave
obtained by summing these component periodic waves

Summing of waves by means of vector diagram. Each wave is

represented by a vector. The sum of the waves = vector F = the
sum of the vectors f1+f2+f3. The phase angle of the sum is .
The total amplitude of the diffracted wave is the vector sum
(taking into account the different phase angles) of the
contributions from each atom.

Phase (f1)

Phase (f2)

refl
The length of this vector
represents the amplitude, its 1
angle represents the phase.
2
p 0
The resultant amplitude
is the vector sum.

(frefl) is the phase of the resultant

reflection which has an amplitude
represented by the length of the blue
line
 Fourier Transforms
 The Fourier transform provides bridge between Bragg reflection and electron density
map.

 The Bragg reflection, order n, contributes to the electron density map an electron
density wave with a periodicity d/n

 For example the Bragg reflection 300 represents an electron density wave that repeats
three times in the a direction of the unit cell and has an amplitude F(300)

 If the 300 reflection is observed then the electron density repeat three times in the unit
cell repeat.

 If the 200, 300 and 500 Bragg reflections are all observed, the electron density must
equal the sum of the three cosine waves.

 When all such density waves are summed with appropriate relative phases, the
electron density in the crystal is obtained.

 While summing the electron density waves we obtain almost all the information like
F(hkl) and order n (hkl), however to calculate electron density map we need relative
phases of each term which are missing because intensities rather than amplitudes are
measured.

 If the electron density is known correctly, then structure factors and their relative
phases can be computed by Fourier transformation techniques.
 The structure factor

 To compute F(hkl) when atomic coordinates xj, yj, zj for each atom j are
known

A(hkl )  fj cos 2 (hxj  kyj  lzj )

j

B (hkl )  fj sin 2 (hxj  kyj  lzj )

j
 The Structure Factor Equation

Simplified approach
- how waves combine after diffraction
• complete cancellation
• partial cancellation
• constructive interference
Depends on phase difference 
Also on fractional coordinates
hkl
how much the atom scatters x-rays
:
Intensity of the wave is proportional to FF* (where F* is the complex
conjugate of F)

FF* = (fj ei) (fj e-i ) = fj2

and so
I  fj2

Summing the diffracted waves over all atoms, j, in the unit cell gives

Fhkl  f j exp(i j )
j
so

Fhkl  f j exp 2i(hx j  ky j  lz j )

j

Structure factor equation

 This can also be written as:

Fhkl  f j (cos  j  i sin  j )

j

 This can be simplified in structures with a centre of symmetry

= centrosymmetric structures - for every atom at (xj yj zj) there
is an identical atom at (-xj -yj -zj)
 These atoms will have phases +j and -j respectively, and
since sin(- ) = -sin  the sine terms cancel
 so

Fhkl  f j cos 2(hx j  ky j  lz j )

j

The Centrosymmetric structure factor equation

 Example -  - Fe

Fe at (0, 0, 0) and (½,½,½) - centrosymmetric

Fhkl = fFe [cos 2(0 + 0 + 0) + cos2(h/2 + k/2 + l/2)]

= fFe[cos 0 + cos  (h+k+l)]
= fFe[1 + 1] = 2fFe if h+k+l = 2n I=4fFe2
= fFe[1 + (-1)] = 0 if h+k+l = 2n+1 I=0
Reflections with h+k+l = 2n+1 are systematically
absent
For any bcc lattice, only reflections with
(h+k+l) = 2n are present
 Example - F-centring
Atoms at (0, 0, 0) (½,½,0) (½,0,½) (0, ½,½) -
centrosymmetric but use whole equation as example

Fhkl  f j exp 2i(hx j  ky j  lz j )

j
Fhkl = fFe [exp 2i(0) + exp2i(h/2 + k/2) +
exp2i(h/2 + l/2) + exp2i(k/2 + l/2) ]
= fFe[1 + exp i (h+k) + exp i (h+l) + exp i (k+l)]

Remember:
exp i (n) = 1 if n even
exp i (n) = -1 if n odd
Fhkl = fFe[1 + exp i (h+k) + exp i (h+l) + exp i (k+l)]

??

If h,k,l all even, then Fhkl = 4f I=16f2

If h,k,l all odd, then Fhkl = 4f I=16f2

If mixture?
(3 2 2) : Fhkl = [1 - 1 - 1 + 1] = 0

(3 3 2) : Fhkl = [1 + 1 - 1 + 1] = 0

So reflections only present if h,k,l all odd or all even

 Example: CsCl

 CsCl is primitive.
 Atoms at (0,0,0) (Cs) and (½,½,½) (Cl)
 All rest generated by symmetry/translation

So Fhkl = fCs cos 2 (0) + fCl cos 2 (½h + ½k + ½l)

Fhkl = fCs + fCl cos  (h + k + l). Two cases:

If h+k+l = 2n Fhkl = fCs + fCl

If h+k+l = 2n+1 Fhkl = fCs - fCl
Reflections with h+k+l = 2n are strong
Reflections with h+k+l = 2n+1 are weak
CsCl cf “CsCs” – P vs I
CsCl (Davey, W.P.;Wick, F.G. (1921) Physical Review 17, 403-404)
Lambda: 1.54180 Magnif: 1.0 FWHM: 0.300
Space grp: P m -3 m Direct cell: 4.1200 4.1200 4.1200 90.00 90.00 90.00

011
001

112
002

012

0 0132 2
111

013

123
022

113
222
023

004
0 10 20 30 40 50 60 70 80 90 100

"CsCs" - mythical bcc material

Lambda: 1.54180 Magnif: 1.0 FWHM: 0.300
Space grp: P m -3 m Direct cell: 4.1200 4.1200 4.1200 90.00 90.00 90.00
011

112
002

013

123
022
0 01 32 2

222

004
001

111

012

113

023

0 10 20 30 40 50 60 70 80 90 100
Choice of origin

Arbitrary, so we could have Cl at (0,0,0) and Cs at

(½,½,½)

What effect does this have on the structure factor equation? The intensities?
 Example - NaCl
4 sodium ions and 4 chloride ions per unit cell
2 2 2 2 2 2
, 0, 0. 0, , 0; , , ; 0, 0, ; Cl
1 1 1 1 1 1
2 2 2 2 2 2
0, , ; , 0, ; 0,0,0; , , 0; Na
1 1 1 1 1 1
the crystal structure is centrosymmetric, and therefore B(hkl) 0
only when h  k, k  l, l  h are all even or all odd , A(hkl)have a non-zero value

F (hkl )  A(hkl )  fNa cos 2 (0)  fNa cos 2 (h 2  k 2) 

fNa cos 2 (h 2  l 2)  fNa cos 2 (k 2  l 2)  fCl cos 2 (h 2  k 2  l 2)
 fCl cos 2 (l 2)  fCl cos 2 (k 2)  fCl cos 2 (h 2)
 Example - NaCl
F (hkl )  A(hkl )  fNa cos 2 (0)  fNa cos 2 (h 2  k 2) 
fNa cos 2 (h 2  l 2)  fNa cos 2 (k 2  l 2)  fCl cos 2 (h 2  k 2  l 2)
 fCl cos 2 (l 2)  fCl cos 2 (k 2)  fCl cos 2 (h 2)

hkl F(hkl) systematic description F(hkl) c F(hkl)

o

111 4(fNa - fCl) h,k,l all odd 19.0 20.6

222 4(fNa  fCl) h,k,l all even 53.3 52.9
333 4(fNa - fCl) h,k,l all odd 7.3 8.1
120 0 h odd, k even , l even 0.0 0.0
Comparison: NaCl vs KCl
NaCl (Hull, A.W. 1919)
Lambda: 1.54178 Magnif: 1.0 FWHM: 0.200
Space grp: F m -3 m Direct cell: 5.6400 5.6400 5.6400 90.00 90.00 90.00

002

NaCl Fhkl = 4fNa + 4fCl if h,k,l all even

022
Fhkl = 4fNa - 4fCl if h,k,l all odd

222

024

224
111

004

1 13 53 3
113

133
20 30 40 50 60 70 80 90 100

KCl (Hull, A.W. 1919)

Lambda: 1.54178 Magnif: 1.0 FWHM: 0.200
Space grp: F m -3 m Direct cell: 6.2800 6.2800 6.2800 90.00 90.00 90.00
002

KCl As mentioned before, K+ and Cl-

are isoelectronic
022

So 4fK - 4fCl ~ 0
222

024

224

0 0 62 4 4
004

1 13 53 3

044
111

113

133

135

20 30 40 50 60 70 80 90 100
 Example: Polonium!
 Polonium is primitive cubic.
 Atoms at (0,0,0)
 All rest generated by
symmetry/translation

Fhkl  f j cos 2(hx j  ky j  lz j )

j

So Fhkl = fj cos 2 (h0 + k0 + l0)

= fj cos (0) = fj and I = k f j2 (where k is a known constant)

To finally get the diffraction pattern we would need to know the form of fj
with  (Z=84) and the unit cell parameters.
Polonium
Polonium (Desando, R.J.;Lange, R.C. Journal of Inorganic and Nuclear Chemistry)
Lambda: 1.54180 Magnif: 1.0 FWHM: 0.300
Space grp: P m -3 m Direct cell: 3.3590 3.3590 3.3590 90.00 90.00 90.00

0 10 20 30 40 50 60 70 80 90 100 110 120

Example: Copper
 Copper is face centred cubic.
 Atoms at (0,0,0), (½,½,0), (½,0,½), (0,½,½)

Three cases to consider

h,k,l all odd
h,k,l all even
h,k,l mixed (2 odd, 1 even or 2 even, 1
odd)

Thus, reflections present when …

Generally true for all face centred structures
 More Complex Cases
Ti metal is h.c.p.
Atoms at (0, 0, 0) and at (1/3, 2/3,1/2)

Fhkl = fTi [exp 2i(0) + exp2i(h/3 + 2k/3 + l/2)]

= fTi [1 + exp2i(h/3 + 2k/3 + l/2)]

Can’t simplify this - would have to substitute in hkl values

e.g. (100) Fhkl = fTi [1 + exp(2/3)i]
= fTi[1 + cos(2/3)  + isin(2/3) ]
= fTi [0.5 + 0.866i]
and similarly
(010) Fhkl = fTi [0.5 - 0.855i] etc.
 The phase difference, 
For a given direction [specified by (hkl) d and  so as
to satisfy Bragg’s Law] we consider X-rays scattered
by all atoms in the unit cell

Consider a set of lattice

planes:
For the (100) planes, A
and A’ scatter in phase
because their phase
difference is one
wavelength (2 radians)

An atom at D has fractional x coordinate of ½

The phase difference between waves diffracted from A and

D is ½ . 2 =   atoms A and D are out of phase

Atom B has a general fractional coordinate x and thus a

phase difference relative to A of 2x for (100) planes
If we now take
the (200)
planes:

Atoms A and D now have a phase difference of 2

for the (200) reflection whereas phase difference =
 for (100)
(In order to obey Bragg’s Law, if d is halved then
sin must double)
Halving d [(100)  (200)] doubles the relative
phase difference

Atom B has a phase difference relative to A of

4x for (200) planes c.f. 2x for (100) planes

So for a general (h00) reflection, distance between

(h00) planes is (a/h) {orthogonal systems}
Phase difference, , between A and B is thus:
 = 2hx
For (h00), y and z coordinates don’t affect  values
 The phase difference, 

Generalize in 3-d:

j = 2 (hxj + kyj + lzj)

where:  = phase difference for atom j
j

hkl = Miller index of plane

(xj yj zj) = fractional coordinates of atom j

 is sometimes known as the geometric structure factor

j
 Example j = 2 (hxj + kyj + lzj)
Phase differences for atoms in body centred
lattice
Atoms at (0, 0, 0) (½,½,½)
1 = 2(0 + 0 + 0) = 0
2 = 2(½h + ½k + ½l)
=  (h+k+l)
If h+k+l = odd number (2n+1)

 out of phase  complete cancellation

If h+k+l = even number (2n)

 in phase  only observe reflections with h+k+l = 2n

[c.f. systematic absences]

Summary,
 Each atoms contributes intensity to each Bragg
reflections by an amount that depends on its
position in the unit cell, its scattering power and the
scattering angle.
 We need to measure many Bragg reflections than
the parameters (position (3) and thermal (6), total 9
for one atoms).
 The reflection to parameter is generally around 10.
 Electron density map
 The electron density in a crystal precisely fits the definition of
periodic function in which exact repeat occurs at regularly fixed
intervals in any direction (the crystal lattice translation).
 Therefore the electron density in a crystal with a periodicity d can
be described by a Fourier synthesis in which each component
cosine wave (electron density wave) has a periodicity (i.e.
wavelength) d/n and amplitude of the nth order Bragg reflection.
 A electron density map is calculated by Fourier synthesis.

1
 ( xyz )     F (hkl ) cos 2 (hx  ky  lz  hkl )
V h k l
This electron density (xyz) at a point x, y, z in the unit cell
volume V, is expressed in electrons per cubic Å and is highest
near atomic centers.
In X-ray diffraction experiment, the number of waves that must be
summed is very large.
 The equation of the electron density at any point (x,y,z), in the unit cell
then involves the structure factor amplitude and relative phase angle
for each brag reflection.

F (hkl ) structure factor amplitude

hkl relative phase angle
If a single point within a unit cell is chosen with fractional coordinate
x,y,z (distance xa ║a; distance yb ║b and distance zc ║c), the electron
density (xyz) at that point is calculated by the equation…
1
 ( xyz )     F (hkl ) cos 2 (hx  ky  lz  hkl )
V h k l

The right hand side of this equation involves the summation of all the
measured Bragg’s reflections.
If the intensities of 6,000 diffracted beams are measured, there will be
6,000 F(hkl)  values included in this summation for just one point.

In practice, the electron density map is calculated at regular interval of the

asymmetric unit.
The electron density is measures in Å3 and the summation is divided by the
unit cell volume V.
Contributions to terms in Fourier
synthesis
(a) Individual terms from 000 to 10 00
(h = 10, k = 0, l = 0) are represented
with positive area shaded.
These 10 electron density waves
combine to give the electron density
shown at the bottom of the diagram
The electron density is dependent on
the phases (+ = 0, – =180) which are
000 +; 100 –; 200 –; 300 +; 400 –; 500
–; 600 +; 700 –; 900 +; 10 00 –
Effect of successive addition

At the bottom of this diagram

is shown the effect of adding
the 000 ad 100 terms.

As more terms are added the

two peaks of electron density
becomes more distinct and
the resolution of the image is
increased.
Extra Reading.
 Argand Diagrams
These diagrams are called Argand diagrams, where the
horizontal axis is real and the vertical axis is imaginary.
These end up being a much simpler way of adding waves
because each wave can easily be represented as a vector.
The length of each vector is fj, and the phase relative to the
origin is provided by the angle (f).

From Euler: eif = cos(f) + isin(f); Thus:

exp(-inpx) = cos(npx) – isin(npx)
And: exp(inpx) + exp(-inpx) = 2 cos(npx)
exp(inpx) - exp(-inpx) = 2i sin(npx)
 Argand Diagrams
Here are some more properties of complex numbers and Argand diagrams
that end up being helpful in the understanding of structure factors. In
particular, notice that the phase angle can be easily determined from
tan(B/A) if we know the values A and B. Also notice that to square a
complex number, it must be multiplied by its complex conjugate!

z = a + ib = |z| (cos + isin),

where  is the angle between z and the real axis.
|z| = (a2 + b2)1/2 = [(a + ib)(a - ib)]1/2 = (z z*)1/2

complex conjugate
 Algebraic method for summing of waves
The displacement of n cosine waves xn can be represented as

x1 c1 cos(   1) cn is amplitude (maximum displacement)

of the wave
x 2 c 2 cos(   2)  is proportional to the time since a
travelling wave has pass the origin, which
 is constant.
n is the relative phase angle of the wave
xn cn cos(  n)
When the two waves superimposed , the displacement xr is
the sum of the individual displacement

xr  x1  x 2 c1 cos(   1)  c 2 cos(   2)

xr c1(cos  cos  1  sin  sin  1)  c 2(cos  cos  2  sin  sin  2)
xr (c1 cos  1  c 2 cos  2) cos   (c1 sin  1  c 2 sin  2) sin 
 Algebraic method for summing of waves
If we write the amplitude cr and phase r of the resulting wave such that

cr cos r c1 cos  1  c 2 cos  2  cn cos n

n

cr sin r c1 sin  1  c 2 sin  2  cn sin n

n

 xr cr cos r cos   cr sin r sin  cr cos(  r )

Therefore the waves obtained has the same frequency as
the two original waves and its phase is measured relative to
the same origin as that of the original waves.
This wave is represented by the equation:

cr sin r  n cn sin n
tanr  
cr cos r  n cn cos n
 Algebraic method for summing of waves

The amplitude of the resultant wave is cr

1
cr [(cr cos r )  (cr sin r ) ]
2 2 2

1
[( n cn cos n) 2  ( n cn sin n) 2 ] 2
Summing of waves by numerical method
 Summation of two waves
with periodicities 3 and 2
respectively, (3 0 0) and (2 0
0). Values of displacement of
the waves indicated by
vertical lines.
 At each point along the
horizontal axis, the
displacement of each wave
can be measured as the
distance from this axis in a
direction parallel to the
vertical axis.
 To sum two or more waves,
the displacement values can
be added point by point and
the shape of the composite
wave can be drawn.
 Fourier Series
 Any periodic function such as electron density in a crystal
which repeats from unit cell to unit cell, can be represented
as the sum of cosine (and sine) functions of appropriate
amplitude, phase and periodicities (frequencies).
 Fourier showed that a continuous periodic function can be
described in terms of the simpler component cosine (or
sine) functions referred as Fourier series.

f ( x) a 0  a1 cos 2 ( x)  a 2 cos 2 (2 x)  ......  ah cos 2 (hx)

 b1 sin 2 ( x)  b 2 sin 2 (2 x)  ......  bh sin 2 (hx)
h
f ( x) a 0   (ah cos 2 (hx)  bh sin 2 (hx)
1
where h is an integer, ah and bh are constants, and x is a fraction of a period

A one-dimensional Fourier series represents a periodic function in one

dimension. The function can be broken up into even [f(-x) = f(x)] and
odd [f(-x) = - f(x)] components. For the even part only cosine terms are
applicable and for the odd part only sine.
 Fourier Series
Fourier series in exponential form (1D)

f ( x)  Ch e 2 ihx e i ( hx ) cos (hx)  i sin (hx)

h

Fourier series in exponential form (3D)

f ( x, y, z )    Chkl e 2 i ( hx ky lz )

h k l
 Fourier Analysis
 Fourier analysis is the mathematical process of dissecting
the periodic function into its simpler component cosine
waves, thus showing how the periodic function might have
been put together.

 Breaking the regularly repeat function into its component

simple cosine waves. Fourier analysis gives for each
component wave, its amplitude, its frequency and its phase
related to the chosen origin.
 Fourier Synthesis
 Fourier synthesis is the reverse of Fourier analysis. It
involves the summation of waves of known frequency,
amplitude and phage in order to obtain resultant periodic
function.

 Summing a series of waves of different amplitude,

frequency and relative phases. Because the waves are
periodic, their sum is also periodic.
 Fourier Transform

 The electron density (xyz) is expressed as Fourier series with the

structure factor F(hkl) as coefficient with V as unit cell volume.

1
 ( xyz )     F (hkl ) cos 2 (hx  ky  lz  hkl )
V h k l

 The structure factor can be expressed in terms of electron

density.
 The mathematical way of expressing these analogs involves
Fourier transforms also called as Fourier inversions.
 The Fourier transformation allows to flip between real
space and diffraction space.
 It is the mathematical way of transforming Bragg reflection
data to an electron density map.
 Fourier Transforms
consider two equations
 
2ixy
f(x)  e g ( y )dy and g(y)  e  2ixy f ( x)dx i 1
 

g(y) is the Fourier transform of f(x) and f(x) is the inverse transform of g(y).

In a similar way electron density (xyz) is the Fourier transform of the array
of structure factors F(hkl) and array of structure factors F(hkl) is the inverse
Fourier transform of the electron density (xyz).

structure factor F (hkl )   ( xyz )e i dv &

V

1
electron density  ( xyz )   F (hkl )e  i dv
V hkl
where  2 (hx  ky  lz )
STRUCTURE FACTOR FT ELECTRON DENSITY
 Fourier Transforms

 The Fourier transform equation show that the electron density is the
Fourier transform of the structure factor and the structure factor is
the Fourier transform of the electron density.
 If the electron density can be expressed as the sum of cosine waves
then, its Fourier transform corresponds to the sum of the Fourier
transforms of the individual cosine waves.
 The inverse theorem states that the Fourier transform of the Fourier
transform of an object is the original object.
 This expression can be used go back and forth between reciprocal
space (structure factors) and real space (electron density) and visa-
versa.
Fourier Transforms
 Graphical examples of the
Fourier transforms of (a) a
cosine and (b) a sine function.
 Note that the Fourier
transform contains information
on phase but this information
is lost when intensities are
measured.
 The term “real” and
“imaginary” derives from the
presence of i   1

in the Fourier transform

equation.
Fourier Transforms

 The Fourier transforms of the

200, 300 and 500 electron
density waves.
 shown on left is one unit cell
and an electron density wave,
and on the right, its Fourier
transform (Bragg reflection).
Fourier Transforms
 Summing Fourier transform of the
Fourier components of an electron
density map to get a representation of
a diffraction pattern.

 (a) the Fourier transform of three

electron-density waves (200, 300 and
500).

 (b) The sum of the electron density

waves in (a) (with relative phases 200,
hkl = 180, 300, hkl = 0 and 500, hkl =
180) gives a diffraction pattern with
intensity at 200, 300, and 500 but no
phase transformation.

 The sign of the results of the Fourier

transformation are lost when the
values of F(hkl) 2 are calculated.
Fourier Transforms

The diffraction pattern of a

crystal is the diffraction
pattern of the contents of
one unit cell multiplied by
the Fourier transform of the
crystal lattice (the
reciprocal lattice).

The diffraction pattern of

the two objects is a
diffraction pattern of one
object multiplied by the
Fourier transform of two
objects, which is a series of
fringes.

The relationship between a

crystal structure and its
diffraction pattern in terms
of FT, convolution and
multiplications.
Fourier Transforms
The overall scheme of
crystal structure
determination in one
dimension.

(a) Atomic structurre.

(b) Bragg reflection that are

measured

(c) Phases assigned to give

electron density waves
with the correct phases
hkl and amplitudes
F(hkl) .

(d) The summation of

density waves to give
an electron density map

(e) This electron density

map has peak at atomic
position.