**S. C. Wallwork**

**University of Nottingham, England**

In X-ray crystallography the structure factor *F*(*hkl*) of any X-ray
reflection (diffracted beam) *hkl* is the quantity that expresses both the
amplitude and the phase of that reflection. It plays a central role in the
solution and refinement of crystal structures because it represents the
quantity related to the intensity of the reflection which depends on the
structure giving rise to that reflection and is independent of the method
and conditions of observation of the reflection. The set of structure
factors for all the reflections *hkl* are the primary quantities necessary for
the derivation of the three-dimensional distribution of electron density,
which is the image of the crystal structure, calculated by Fourier methods.
This image is the crystallographic analogue of the image formed in a
microscope by recombination of the rays scattered by the object. In a
microscope this recombination is done physically by the lenses of the
microscope but in crystallography the corresponding recombination of
diffracted beams must be done by mathematical calculation.

The way in which the separate scattered or diffracted rays combine to form an image depends on three factors associated with each ray:

- (a)
- the direction,
- (b)
- the amplitude,
- (c)
- the phase.

In the physical recombination of rays by the lenses of a microscope these
three pieces of information about each ray are retained and used automatically
in the recombination process. In X-ray crystallography, the
diffracted beams are separately observed and their intensities measured as
the blackness of spots on an X-ray film or by direct quantum counting in
a diffractometer. By identifying the Miller indices (*hkl*) of the crystal
plane giving rise to each diffracted beam, the direction of the beam is
specified. From the measured intensity of the beam its amplitude may
readily be deduced. So two of the three necessary pieces of information
about each beam are known, but unfortunately there is no method
available yet for observing the phase of each diffracted beam, which is the
third piece of information needed before mathematical recombination is
possible to produce an image of the structure. This constitutes what is
known as the phase problem in crystallography.

The solution of a crystal structure therefore consists of applying some
technique for obtaining the approximate phases of at least some of the
X-ray reflections, and the process of structure refinement is one in which
the knowledge of phases is extended to all reflections and is made as
accurate as possible for all reflections. Apart from the direct methods of
obtaining some initial phases, both the solution and refinement processes
depend on the ability to calculate structure factors for a proposed
approximate arrangement of some or all of the atoms in the crystal
structure. This is the subject of this pamphlet. It will be seen that it is
possible to calculate simultaneously both the amplitude and
phase of each beam that would be diffracted by the proposed
structure. Since the phases cannot be compared with any observable
quantities, the validity of the proposed structure must be tested by
comparison of the calculated values of the amplitudes of the structure
factor *F _{c}* with the observed amplitudes |

where the summation is usually taken over all the reflections giving significant intensities. Because of random errors in the observed structure factor amplitudes |

A structure factor represents the resultant X-ray scattering power of the whole crystal structure, though, since the whole structure consists of a large number of unit cells all scattering in phase with each other, the resultant scattering power is actually calculated for the contents of one unit cell only. The structure factor therefore represents the resultant amplitude and phase of scattering of all the electron density distribution of one unit cell. The amplitude is calculated as the number of times greater it is than the amplitude of scattering from an isolated electron. The phase is calculated relative to a phase of zero for hypothetical scattering by a point at the origin of the unit cell. The resultant is calculated as a superimposition of waves, one from each atom in the unit cell, each wave having an amplitude which depends on the number of electrons in the atom and a phase which depends on the position of the atom in the unit cell.

Before seeing how to do this calculation in detail we must first see how
wave motions of different amplitudes and phases can be combined. We
consider the simplest case of the addition of a wave of amplitude *f _{1}* and
phase and a wave of amplitude

The sum of these two wave motions is simply a wave of the same phase
with amplitude (*f _{1}* +

When the first wave has a phase angle relative to the radius at the
angle and the second wave has a phase angle relative to the same
radius, the two component waves and their resultant are as shown in Fig.
1(*b* ). The resultant now has an amplitude which is less than
(*f _{1}* +

and the displacement for the resultant wave is given by

When the cosine terms are expanded this becomes

As can be seen from Fig. 1 the resultant wave is another cosine wave of the same frequency as the component waves but of different phase which we will call . It can therefore be represented by:

Expanding this, we have

Comparing equation (2) with equation (1), we see that

To find the amplitude |*F*| and phase of the resultant wave we note that:

and

In general, to find the resultant amplitude and phase for a wave
composed of *n* cosine waves, of which a typical component *j* has
amplitude *f*_{j} and phase , we have

and |

This addition of components may be represented conveniently on a
vector diagram as in Fig. 2, where the example of the addition of the
same two components is again shown. It can be seen on this diagram that
*A*' is the algebraic sum of the terms and *B*' is the algebraic sum
of the terms. The resultant vector *F* is the vector sum of the two
components and the square of its amplitude, |*F*^{2}|, is shown by Pythagoras'
theorem to be given by (*A*')^{2} + (*B*')^{2}. The direction or phase of the
resultant is given by the angle , whose tangent is equal to *B*'/*A*'.

It is conventional to represent the amplitude and phase of a wave by a
complex number which may be expressed in the form *a* + *ib* or as . In these representations, *a* or
is the real part
of the complex number and *ib* or is the imaginary part. This is
quite consistent with the vector representation of Fig. 2 in that *A*'
represents the real part *a* of the complex wave *F* and *iB*' is the imaginary
part *ib*. The horizontal axis of Fig. 2 should therefore be regarded as the
real axis and the vertical axis as the imaginary axis of the conventional
Argand diagram for representing complex numbers. In the exponential
form of a complex wave, , the angle corresponds to the phase angle of Fig. 2 and *x*
corresponds to the amplitude |*F*|.

Having seen how waves may be added to give a resultant wave we are
now in a position to apply this procedure to the addition of waves
scattered by the different atoms of a unit cell to give a resultant structure
factor *F*. We need to consider the amplitude *f* of the scattering from each
atom and its phase . Both these quantities are best approached from the
point of view of the Bragg treatment of X-ray diffraction, which will first
be outlined.

The Braggs, father and son, considered the diffraction of X-rays by a crystal to be more conveniently thought of in terms of reflection from regularly spaced, parallel planes in the crystal. Like any reflection process the angle between the incident beam and the reflecting plane is equal to the angle between the reflected beam and the plane. Unlike specular reflection, however, only certain angles of incidence and reflection will give rise to appreciable intensity in the reflected beam. These are the angles for which the rays reflected by successive planes in the crystal differ in phase by a whole number of wavelengths. (This restriction arises because the problem is really one of diffraction.) The difference in phase is found by calculating the difference in path length for two successive rays.

Consider first two rays of the incident beam that strike successive
crystal planes at points *O* and *B*, respectively, where *OB* is perpendicular
to the crystal planes (Fig. 3*a* ). The extra distance travelled by the lower
ray is calculated by drawing perpendicular wave-fronts *OA* and *OC* to
the incident and diffracted beams, respectively. It is seen to be *AB* + *BC*.
Since is the angle between *AB* and the crystal plane and between *BC*
and the crystal plane, is also the angle between the perpendicular to
*AB* (i.e. *OA*) or to *BC* (i.e. *OC*) and the perpendicular to the crystal planes
(i.e. *OB*). This is shown on the enlarged part of the diagram in Fig. 3*b* .
Now, from the triangles *ABO* and *BCO*:

since

Secondly we must show that the path difference is the same for two
rays reflected from two successive crystal planes irrespective of the points
on the planes at which they strike the planes. Consider the two rays
reflected from the top plane at the points *P* and *O*. To check that there is
no path difference between these two rays we construct the perpendiculars
*PQ* and *OR*. The distance travelled by the ray reflected at *O* between
the perpendicular wave fronts *PQ* and *OR* is *QO*. This is equal to
. The distance travelled by the ray reflected at *P* between the
same two wave-fronts is *PR*. However, since the angle *RPO* is also
, *PR* is also equal to . The two rays
are therefore in phase with each
other throughout. This also means that if the phase difference between
the rays reflected at *O* and *B* is after reflection, then the phase
difference between the rays reflected at *P* and *B* is also after
reflection. This establishes the principle that the phase difference between
rays reflected from parallel planes in a crystal depends on the distances of
the points of reflection measured perpendicular to the planes and not on
the separation of the points of reflection measured parallel to the planes.
Use is made of this principle both in considering how the amplitude of
scattering of an atom depends on the Bragg angle and also in calculating how the phase of the scattered beam from each
atom depends on its position in the unit cell.

If all the electrons in an atom were concentrated at one point, the
amplitude of the X-rays scattered by the atom would simply be *Z* times
the amplitude scattered by a single free electron, where *Z* is the atomic
number of the atom. In fact, the electrons form a diffuse cloud of varying
density, spherical in symmetry to a first approximation, but with quite
high electron densities at, say, half the conventional atomic radius away
from the centre of the atom. It is possible for the X-rays scattered from
one part of the atom to be out of phase with those scattered from another
part so that their contributions to the total scattering cancel instead of
adding. The total amplitude of scattering by an atom will therefore, in
general, be less than *Z* and will depend on the spacing of the parallel
diffracting planes for the X-ray reflection under consideration.

This may be understood by reference to Fig. 4. On the left is shown the
situation where the spacing *d _{1}* between the Bragg planes

We must now consider how the phase of scattering by an atom, as a
contribution to a total structure factor *F*, depends on the position of the
atom in the unit cell. The principle of the method is that the rays reflected
by successive Bragg planes are one wavelength out of phase with each
other and therefore differ in phase angle by radians or 360. The
hypothetical ray reflected from the origin of the cell always defines the
phase angle zero, so the points of intersection of the plane *hkl* with the
cell axes correspond to a phase of radians or 360. The phase for the
scattering by any atom in the unit cell (considered for this purpose as
being at the point of its centre) is therefore given by its distance measured
perpendicularly between a plane through the origin parallel to the plane
*hkl* and the plane *hkl* itself. (It will be remembered that the phase is
independent of the position parallel to the Bragg planes.) The calculation
of the phase is best illustrated in two dimensions, as in Fig. 6.

The *x* and *y* axes of a two dimensional cell are shown intersected by
the Bragg plane (actually a line) defined by the Miller indices *h*, *k*. From
the definition of Miller indices, the intersection along the *x* axis occurs at
a distance *a*/*h* from the origin *O* and the intersection along the *y* axis
occurs at *b*/*k* where *a* and *b* are the unit cell dimensions along the *x* and
*y* axes, respectively. The perpendicular spacing *d* between this plane and
the parallel plane through the origin is given by the distance *OR*.
Consider an atom at the point *T*, having coordinates *x* and *y* in the cell.
We wish to know how far *T* is perpendicularly from the plane through *O*
towards the plane through *a*/*h*, *b*/*k*, compared with the total
perpendicular distance between these planes. It is convenient to measure all the
perpendicular distances along the line *OR*, so the component of the
distance due to the *x* coordinate is obtained by projecting the distance *x*
onto *OR* as *OP*, and the component due to the *y* coordinate is obtained
by projecting *y* onto *OR* as *PQ*. The total perpendicular distance of *T*
from the plane through *O* is therefore *OQ* and it is calculated as follows:

But, from the triangle defined by *O*, *R* and the point *a*/*h*,

and, from the triangle defined by

So

Now *OR* or distance *d* corresponds to a phase change of radians. So
*OQ* corresponds to a phase change of radians. This is therefore
equal to radians and it represents the phase of scattering
from the point *T* compared with zero phase at the origin of the cell.

When this calculation is extended to three dimensions, the intercept of
the plane *hkl* with the crystallographic *z* axis at the point *c*/*l* and the
projection of *z* on the perpendicular from *O* to the plane must also be
taken into consideration. The phase of scattering by an atom at the point
*x*, *y*, *z* is then given by

This is therefore the expression for the calculated phase angle for use in equations such as (3) and (4). The amplitude

Or, in exponential form, the structure factor may be expressed as:

In each case the summation is taken over the

In practice, any one atom in the unit cell is related to other atoms in
the cell by the operation of the various symmetry elements. By taking
account of the relationship between the coordinates of these
symmetry-related atoms, formulae can be derived expressing the sum of the
factors and the sum of the factors for the whole of this group of
symmetry related atoms. These sums are usually called *A* and *B*
respectively. The whole sum, *A* or *B*, is then multiplied by the
atomic scattering
factor which again, in practice, is corrected for thermal motion of the
atoms which further smears out the electron cloud and causes a more
rapid drop in *f*_{j} with than that illustrated in Fig. 5. Then:

where the sum is taken over the atoms of one asymmetric unit only. The details of these extensions to the basic principles of the calculation of structure factors are outside the scope of this pamphlet but formulae for

Finally it should be mentioned that whenever a collection of atoms for
which a structure-factor calculation is being performed has a centre of
symmetry, the resultant structure factor is always entirely real and hence
the associated phase angles are always either 0 or . That this is so may
easily be seen by dividing the structure up into centrosymmetrically
related pairs. For every atom at *x*, *y*, *z*, there will be one at -*x*, -*y*,
-*z*
and hence the imaginary parts, *B*', of the structure factor, since they involve
a sine term, will be opposite in sign and cancel out.

**Copyright © 1980, 1997 International Union of Crystallography**