Form Factor and Structural Factor

Solid State Physics (Kittle)

Crystalline Solids
Number density in 1D
n(x) = _
p
n
p
exp_i
2 p
a
Reciprocal Point
AllowedterminFourier Series
x
in 3D
n(r) = _
G
n
G
exp_i G

. r

= n
G
=
1
V
c
_
dVn(r) exp_i G

. r

Diffraction Condition
Scattering Amplitude
F =
_
dVn(r) expi (k k '). r

= _
G
_
dVn(r) expi (G Ak). r

, k + Ak = k ' , k + G = k ' = 2 k

= G
2
= G
2
N number of cells
F
G
= N
_
dVn (r) exp_i G

. r

= N S
G
n(r) = _
j=1
s
n
j
r

S
G
= _
j
_
dVn
j
r

j
exp_i G

. r

if = r

j
S
G
= _
j
exp_i G

.r
j

_
dVn
j
() exp_i G

Atomic FormFactor
S
G
= _
j
f
j
exp _i G

.r
j

.r
j

= (v
1
b
1
+ v
2
b
2
+ v
3
b
3
).|x
j
a
1
+ y
j
a
2
+ z
j
a
3
] and b
i
a
j
= 2
ij
S
G
= _
j
f
j
exp2 i |v
1
x
j
+ v
2
y
j
+ v
3
z
j
]j
f
j
scattering power of jth atom
f
j
=
_
dVn
j
(r) exp_i G

. r

=
_
dVn(r) exp(i Gr cos)
f
j
= 4
_
dr n
j
(r) r
2
Sin(Gr)
Gr
in spherical corodinates
at r =0
f
j
= 4
_
dr n
j
(r) r
2
= Z
Non Crystalline solids
The x-rays or neutron diffraction pattern of an amorphous materials such as a liquid or a glass consists of one or
more broad diffuse rings. The result tells that a liquid does not have a unit of structure that repeat itself indentically
at periodic intervals in three dimensions. From a typical liquid or glass diffraction pattern, containing three or four
diffuse rings, the only qunatity which can be determine directly in the radial distribution function (RDF). Therefore
the scattered amplitude from an amorphous material is described by
S(Ak) = _
m
f
m
expi Ak r

The scattering intensity at scattering vector is given by

I = S
-
S = _
m
_
n
f
m
f
n
expi Ak r

m
r

n
= _
m
_
n
f
m
f
n
exp(i Ak r
mn
Cos )
in an amorphous specimen the vector r

m
r

n
may take on all orientations, so the avergae factor over a sphere
(exp(i Ak r
mn
Cos )) = (exp(i K r
mn
Cos )) =
1
4
2
_
1
+1
exp(i K r
mn
Cos ) d(cos) =
Sin Kr
mn
Kr
mn
I = _
m
_
n
f
m
f
n
Sin Kr
mn
Kr
mn
MonoAtomic Amorphous Materials
for only one type , f
m
= f
n
= f . For a specimen of N atoms. The sum runs over all atoms except the origin atom m
=n
I = N f
2
_1 + _
m
Sin Kr
mn
Kr
mn

If r

is the concnetration of atoms at distance r from a reference atom

I = N f
2
_1 +
_
R
0
dr 4 r
2
(r)
Sin Kr
Kr

Let
0
denotes the average concentration
2 Untitled-1
I = N f
2
_1 +
_
R
0
dr 4 r
2
(r)
0

Sin Kr
Kr
+

K
_
0
R
4 r sin (Kr) dr
The 2nd integral in eq 4 gives the scattering from a uniform concentration and may be neglected for very small
angle, it reduces to a delta function at the origin as R o .
the liquid structure factor
S(K) = I f N f
2
S (K) = 1 +
_
o
0
dr 4 r
2
(r)
0

Sin Kr
Kr
Radial distribution function g(r){two atom corelation function} is
(r) = g(r)
0
S(K) = 1 + 4
0 _
o
0
dr r
2
g(r) 1
Sin Kr
Kr
S (K) = 1 +
0 _
dr[g (r) 1] exp _i K

in 3D
g (r) 1 =
1
8
3

0
_
d K

_S_K

1 exp_i K

g (r) 1 =
1
2
0
r
_
d K

_S_K

1 K

Sin (K r)
Scattering Correlation Function
1: Neutron Scattering: A Non destructive microscope for seeing inside matter (Roger Pynn)
2: The Physics of Amorphous solids, Richard Zallen
3: Introduction to the theory of thermal neutron Scattering. G.L. Squires
4: Correlation in space and time and Born approximation scattering in systems of interacting particles, Van Hove,
Phy rev, 95,1,249(1954)
5: Intoduction to Quantum Mechanics. Vol 2, Claude cohen Tannoudji
All Neutron scattering experiments, scientist measure the intensity of neutrons scattered by matter ( per incident
neutron) as a function of the variable Q and E. The Scattering Intensity I(Q,E) is often called Neutron Scattering
Law.The scattering law can be written in term sof time dependent correlations between the positions of apris of
atoms in the sample. I(Q,E) is proportional to the Fourier trnasform of a function that gives the probability of
finding two atoms a certain distnace apart. The interaction between a neutron and a nucleus may be replace by an
effective potential that is much weaker than an actual interaction called pseudo-potential causes the same scatter-
ing as the actual potenial but is weak enough to be used in a perturbation treatment. In Born Approximation the
probability of a neutron wave vector k

being scattered by a potential V(r

.
) to become an outgoing wave of wavevec-
tor k ' is proportional to
_
_
e
i k.r
.
V(r
.
) e
i k'.r
.
d r
.2
_ = _
_
e
i k Q.r
.
V(r
.
) d r
.2
_
Untitled-1 3
The scattering can also be written as
I|Q, E] =
1
h
k '
k
_
i, j
b
i
b
j _
o
o
< e
i Q.ri(0)
e
i k Q.r
.
j(t)
> e
i (Ef) t
dt
In this eq (2) the nucleus labeled i is at position r
i
at time t = 0 , while the nucleus labeled j is at position r
j
at time
t. The double summation is sum over all of the positions of the nuclei in the sample and the angular brackets <...>
indicate the thermodynaic average over all the possible configurations that the sample could take.
_
i, j
b
i
b
j
< e
i Q.ri(0)
e
i k Q.r
.
j(t)
> = _
i, j
b
i
b
j _
sample
|r
.
r (0) + (r )
j
(t)] e
i Q.r
.
dr
.
Let the nuclei of the sample have same scattering length . Than
Nb
2
_
sample
G(r
.
, t) e
i Q.r
.
G(r
.
, t) =
1
N
|r
.
r (0) + (r )
j
(t)]
where N is the number of nuclei in the sample. The function G|r
.
, t] is zero unless the separation between nucleus i
at time zero and nucleus j at time t is equal to the vector r
.
. Thus, the function tells us the probability that, within
our sample, there will be a nucleus at the origin of our coordinate system att ime zero as well as a nucleus at
position r
.
at time t. therefore G|r
.
, t] is called the time dependent pair correlation function because it describes
how the correlation between the positions of nuclei evolves with time. the scattering law become
I|Q, E] =
Nb
2
h
k '
k
_
o
o
dt
_
sample
G(r
.
, t) e
i Q.r
.
e
i (Ef) t
dr
.
The scattering law is proportional to the space and time Fourier transforms of the time dependent correlation
function.
In eq (2) all the scattering lengths(sampe of single isotopes) will not be equal because the interaction between the
neutron and the nucleus depends on the nuclear spin, and most isotopes have several nuclear spin states. There is
no correlation between the spin of nucleus and its position, therefore the scattering length in eq (2) can be aver-
aged without interfering with the thermodynamic average. Two averages : the avergae value of b and value of b
2
.
The sum in eq(2) can be avergaed over the nucleus spin states
_
i, j
< b
i
b
j
> A
ij
= _
i, j
< b >
2
A
ij
+ _
i, j
| < b
2
> < b >
2
] A
ij
the first term is coherent scattering (diffraction) in which neutron waves scattered from different nuclei interfer
with each other. This type of scattering depends on the distances between atoms(through the integral represented
by A
ij
) and on the scattering vector Q , and it thus gives infromation about the structure of material. The 2nd term
is incoherent scattering , there is no interference between waves scattered by different nuclei. Rather, the
intensities scattered from each nucleus just add up independently.
Elastic coherent scattering tells us about the equilibrium structure, whereas inelastic coherent scattering (E
0) provide information about the collective motions of the atoms, such as those that produce phonons or vibra-
tional waves in a crystalline lattice.
For a sample containing a single isotopes
I(Q) = |b
2
]
coh
< e
i Q.|ri r
.
j]
>
where the position of nucleus labeled i and j are now evaluated at same instant. If the atoms in the crystal were
stationary, the thermodynamic averaging brackets could be removed becuase r
i
r

j
) = d (interplannar
spacing) is constant. but inreality, the atoms in a crystal oscillates about their equilibrium positions and soend only
a fraction of the time at these positions. than
4 Untitled-1
where the position of nucleus labeled i and j are now evaluated at same instant. If the atoms in the crystal were
stationary, the thermodynamic averaging brackets could be removed becuase r
i
r

j
) = d (interplannar
spacing) is constant. but inreality, the atoms in a crystal oscillates about their equilibrium positions and soend only
a fraction of the time at these positions. than
I(Q) = |b
2
]
coh
< e
i Q.|ri r
.
j]
> e
Q
2
<u
2
>f2
= b
coh
_
i
e
i Q.ri
e
Q
2
<u
2
>f2
= S(Q)
where e
Q
2
<u
2
>f2
is called the Debye-waller factro and < u
2
> is the average of the squared displacemtn of nuclei
from their equilibrium lattice sites. Eq(6) gives us the intensity that would be measured in aneutron scattering
experiment . the quantity is called structure factor S(Q).The intensity of the scattered neutrons is proportional to
the square of the densitty of atoms in the atomic planes reqponsible for the scattering. To measure , Bragg Peaks
corresponding to many different atomic planes, we have to pick the neutron wavelength and scattering angle to
satisfy Braggs law and than rotate the crystal until the Bragg diffracted beam falls on the detector.
Debye -Waller Factor
Radial Distribution Function(RDF)
Let D denote the diameter of the balls which we imagine to be arranged in cubic close packing. D then specifies the
nearest neighbor spacing of the site position(Ball Center) of the corresponding FCC lattice. now we introduce a
very small sphere of variable radius r centered on a aprticular lattice site, which has been arbitrary singled out to
serve as the origin. As r increased from 0, no neighboring sites are encountered until r =D, at which the radius of
the spher eintersect the 12 nearest neighbors. This first corodination shell is characterized by values z
1
( is the
number of the neighboring sites it interect = 12 in this case)and r
1
(radius).For FCC there are six neasrest
neighboring sites at dsitance of D 2 from the origin. the second coordinate shell z
2
= 2, r
2
= D 2 , z
3
= 24 , r
3
=
D 3 as in the figure
In general, the spacing between shells (r
i+1
r
i
) decreases with increasing r.
The RDF for a random atom as the origin, (r)dr gives the probability of finding a neighboring atom at a distance
between r and r + dr. for a crystal lattice with each atomic nucleus regarded as clamped to its equilibrium position
(lattice site), the RDF (r) is the sum of the delta functions, with each term corresponds to a coordination shell
J(r) or
clamped xtl
(r) = _
i
z
i
(r) (r r
i
)
Untitled-1 5
The coordination shells are braodened by thermal and zero point motion.
RDF for Glasses
due to short range order in glasses, the form of well defined nearest neighbors and next nearest neighbors
coordination sheels is provided by the presence of the 1st and 2nd peak in RDF.
For a point particles distributed randomly in space with an averaged numbered density n parrticles per unit volume,
the RDF follows the expected number of particles in a shell of volume 4 r
2
dr .

random
(r) = 4 n r
2
the information about the average density appears in RDF in the form of the large r asymptote as dashed line in
figure. another form of RDF is
g(r) = (1f r) (r) 4 n r
RDF is derivable from fourier Transform, from the result of diffraction experiment. The RDF is real space
transformation of I(k) .
Coordination Shells (Number)
The coordination number of systems with disorder cannot be precisely defined.The first coordination number can
be defined using the radial distribution function g(r)
n
1
= 4
_
r0
r1
r
2
g(r) dr
where r
0
is the point r =0 where g(r) =0 and r
1
is the first minimum. therefore, it is the area under the first peak of
g(r).
6 Untitled-1
The 2nd coordination number is
n
2
= 4
_
r1
r2
r
2
g(r) dr
Pair Distribution Function (PDF) Book
PDF g(r) (static PDF) it gives the average particle density with respect to any particle as the origin obtained by
Ft the result for S(Q).
d
2

dHdE
=

coh
4
k '
k
_
_
jj'
(exp |i Q.R
j'
(0)| exp|i Q.R
j
(t)|) exp(i t) dt
the intermedate function I(Q,t)
I (Q, t) =
1
N
_
jj'
(exp |i Q.R
j'
(0)| exp|i Q.R
j
(t)|)
where N is the number of nuclei in the scattering system. and
G(r, t) =
1
(2 )
3
_
I(Q, t) exp(i Q.r) dQ
I(Q, t) =
_
G(r, t) exp(i Q.r) dr (Inverse FT)
S (Q, ) =
1
(2 )
_
I(Q, t) exp(i t) dt
I(Q, t) =
_
S(Q, ) exp(i t) d
Untitled-1 7
G(r, t) =

(2 )
3
_
S(Q, ) exp(i (Q.r t) ) dQd
S(Q, ) =
1
2
_
G(r, t) exp(i (Q.r t)) dr dt
G(r,t) is known as the time dependent pair correlation function of the scattering system. S(Q,) is Scattering
function (Scattering Law).S(Q,) is the FT of G(r,t) in space and time. The I(Q,t) is the FT of G(r,t) in space
and S(Q,) is the FT of I(Q,t) in time. Eq(9) become after using eq(10) and 11
d
2

dHdE
coh
=

coh
4
k '
k
N S (Q, )
for incoherent cross section
G
s
(r, t) =
1
(2 )
3
_
I
s
(Q, t) exp(i Q.r) dQ (self time dependent correlaton function)
S
i
(Q, ) =
1
(2 )
_
I
s
(Q, t) exp(i t) dt (incoherent scattering function)
d
2

dHdE
incoh
=

incoh
4
k '
k
N S
i
(Q, )
The number density of aprticles at position r at time t is known as the particle density operator.
(r, t) = _
j
|r R
j
(t)]
(r, t) =
1
(2 )
3
_

k
(t) exp(i Q.r) dQ =
k
(t) = _
j
exp|i Q.R
j
(t)]
Eq (10) becomes I (Q, t) =
1
N
(
k
(0)
k
(t)) .
k
(t) =
k
(t) (Hermitian)
Diffraction Studies of Noncrystalline
Materials
The diffraction pattern of glassesliquids generates one or more broad diffuse
halos. In glasses each atom possesses permanet neighbors at definite distances
and in definite directions although in genral these vectorial properties
are not the same for any two atoms in theassemlege. fig 1 is the comparsion
of crystal structure with the glass structure of the same materials A
2
O
3
.
8 Untitled-1
Radial Distribution analysis
The intensity of noncrystalline array of atoms at the angle is given by
I = _
m
(_ )
n
f
m
f
n
Sin(sr
mn
)
sr
mn
, s =
4 sin

if the substance consist of one type of atoms and enviromet of one atom is same as any other atom.sine in summa-
tion each atom become a reference point, and ther will be N terms due to interaction of atom with itself. The value
of each of these terms will be unity since in the limit as r
mn
0,
Sin(sr
mn
)
sr
mn
1
I = N f
2
_
m
Sin(sr
mn
)
sr
mn
so eq 2 becomes, where summation excludes the origin atom.
I = N f
2
_1 + _
m
Sin(sr
mn
)
sr
mn

now consider the distribution as continuous function

I = N f
2
_1 +
_
0
o
4 r
2
(r) dr
Sin(sr)
sr

where (r) is the number density of atoms per unit volume at a distance r from the reference atom and
4 r
2
rdr is the number of atoms contained in a spherical shell of radius r and thickness dr. let
0
be the
average desnity of atoms in the sample than eq 4 becomes
I = N f
2
_1 +
_
0
o
4 r
2
(r)
0
dr
Sin(sr)
sr
+
_
0
o
4 r
2

0
dr
Sin(sr)
sr

the 2nd integral is zero except at very small value of s, where the scattering intensity can be resolved from the main
beam and is unobservable. The simple form of eq 4 is
I
N f
2
1 =
_
0
o
4 r
2
(r)
0
dr
Sin(sr)
sr
by fourier integral theorm the expression can be transformed as
r (r)
0
=
1
2
2
_
0
o
si(s) Sin(sr) ds
or
Untitled-1 9
4 r
2
r 4 r
2

0

2 r
r

0

si s Sin sr s i s
I
N f
2
1
More than one kind of atoms
I = N _
p
f
p
2
+ _
m
m= n
_
n
f
m
f
n
Sin(sr
mn
)
sr
mn
wherem,n.... denotes the kind of atoms constituting some appropiate unit of structure, N is the numbe rof units.The
distributionof atoms about any reference atoms as being continuous, let an atomof type m be the reference atom
and suppose the average number of atoms of type m,n... etc lying in a spherical shell of radius r and thickess dr are
a
m
, a
n
...... etc . A weight density function is
4 r
2

mn
(r) dr = _
m
a
m
f
m
I = N__
m
f
m
2
+ f
m _
4 r
2

mn
(r) dr
Sin(sr)
sr
the scattering factor in term of single electron scattering factor
f
m
= K
m
f
e
k
m
= effective number of electrons per atom of type m . and the atom density function can now be expressed

m
(r) = f
e
g
m
(r) , g
m
(r) = electron density function
I = N __
m
f
m
2
+ 4 f
m
2
_
|_
m
K
m
g
m
(r)| r
2
Sin(sr)
sr
dr
the transform become
I
N
_
m
f
m
2
= 4 f
m
2
_
{_
m
K
m
g
m
(r) g
0
r
2
Sin(sr)
sr
dr
apply FT integral
4 r
2
_
m
K
m
g
m
(r) = 4 r
2
g
0 _
m
K
m
+
2 r

_
0
o
si(r) Sin(rs) ds
i(s) =
I
N
_
m
f
m
2
f
e
2
= _
m
Z
m
I
N [_
m
f
m
2
]
1
where Z
m
= atomic number of atoms of type m.
10 Untitled-1