References for this Topic

✿ Clegg, “Crystal Structure Determination”.

Lattices, Reciprocal Lattices ✿ Stout & Jensen, “X-Ray Structure Determination”, 2nd
Edition. Instrumentation discussion is completely
and Diffraction outdated, but still a good text on the subject.
✿ A more authoritative general reference: Giacovazzo, et
Chem 634 al., “Fundamentals of Crystallography”, IUCr Texts on
T. Hughbanks Crystallography.
✿ MIT has a good site (MIT Open Courseware): http://
ocw.mit.edu/OcwWeb/Chemistry/
5-841Fall-2006/LectureNotes/index.htm

1 2

Bravais Lattices Reciprocal Lattices

• Direct Lattice:
– A regular, periodic array of points with a • Reciprocal Lattice: the basis vectors of the reciprocal
spacing commensurate with the unit cell lattice are defined as
dimensions. The environment around each
b×c c×a a×b
points in a lattice is identical. a* = ; b* = ; c* = ; V = (a × b) • c
• The set of direct lattice points can be written as V V V
(vectors): R = ta + ub + vc t,u,v integers (Note: In physics texts, a factor of 2π is usually included
b×c
• V = volume of unit cell e.g., a * = 2π ; !)
V

V = a ⋅ (b × c ) = • The set of Reciprocal Lattice Vectors (RLVs) are

written as K = ha * + kb* + lc*
b ⋅ (c × a ) = c ⋅ (a × b)
i
h, k,l = integers

3 4
 Side by Side (2-D) b b∗

Reciprocal Lattices a a∗
Reciprocal Lattice
• Properties of RLVs: DirectLattice

a i a * = b i b* = c i c * = 1
a* i b = a* i c = b* i a = b* i c = c* i b = c* i a = 0
b∗

Alternatively, these can be regarded as definitions. ∗

a
b

a
In 2 dimensions, we define the RLVs
a * ⊥ b , b* ⊥ a , a i a * = b i b* = 1
• Although they “live in separate universes”, the direct and
reciprocal lattices are in rotational “lock-step”.

5 6

Lattice & Reciprocal Lattice Lattice & Reciprocal Lattice

Example: BCC treated as Primitive Example: BCC treated as Primitive ^ ^
(a/2)(–x^ + y^ + ^z) (1/a)(y + z)

a 1
a=
2
( x̂ + ŷ − ẑ ) az^ a* =
a
( x̂ + ŷ ) (1/a)z^
a 1
b = ( − x̂ + ŷ + ẑ ) a b* = ( ŷ + ẑ )
2 c b a b*
a 1 (1/a)(x^ + z)
^
c = ( x̂ − ŷ + ẑ ) c* = ( x̂ + ẑ )
c* 1/a
2 (a/2)(x^ – y^ + ^z) a (1/a)y^
ay^ (1/a)x^
a*
Use to find Recip. Lattice Basis: ax^ Exercise: Find the reciprocal
lattice of the reciprocal lattice! ^ + ^y)
(1/a)(x
(a/2)(x^ + y^ – ^z)
b×c c×a a×b
a* = ; b* = ; c* = a If we use the conventional cell (which leaves out half the lattice
V V V
points, the reciprocal lattice includes the ‘open’ points too:
V = (a × b) • c
x̂ ŷ ẑ
a = ax̂ ; b = aŷ ; c = aẑ ⇒ a* = ; b* = ; c* =
a a a

7 8
 Interrelationships Interrelationships
• The direct lattice can be partitioned such that all
of the lattice points lie on sets of planes.
Crystallographers classify these sets of planes
using the intercepts on the unit cell axes cut by
the plane adjacent to the plane through the
origin.
• The intercepts are of the form (1/h, 0, 0), (0,1/k, b b*
0), and (0,0,1/l).
a 2a* + 3b*
• These planes are normal to the RLVs a*

intercept: (1/2,0)
K hkl = ha * + kb* + lc*
-3a + 2b
intercept: (0,1/3)

note: (-3a + 2b) •(2a* + 3b*) = 0

9 10

Interrelationships Interrelationships
Reciprocal Lattice lattice planes

DirectLattice
b
K hkl

K
Kˆhkl = hkl
K hkl
θb
θa a - a unit vector
(0,1/k,0)
c
b
(1/h,0,0)
dhkl = (1/h)a•Kˆhkl = (1/h) a Kˆ cosθa
a 2a* + b* d = (1/k)b•Kˆ = (1/k) b Kˆ cosθb
(hkl) plane hkl hkl
(0,0,1/l)

intercept: (1/2,0) (0,1/k, 0)

intercept: (0,1) -(1/h)a + (1/l )c
b
(1/h,0,0) -(1/h)a + (1/k)b
a

11 12
 hkl Planes are normal to Khkl
Kj•Ri products involve no cross terms
and always yield integers c

• For any DLV Ri and any RLV Kj (0,0,1/l)

(hkl) plane

(0,1/k, 0)

(
R i i K j = ( ta + ub + vc ) ⋅ ha + kb + lc * * *
) -(1/h)a + (1/l )c
b
(1/h,0,0) -(1/h)a + (1/k)b
= th + uk + vl = m, an integer a

• Proof: Consider the plane that cuts the cell axes at (1/h,0,0),
2π iR i iK j
⇒ e = 1, for all R i and all K j (0,1/k,0) and (0,0,1/l).
• Two vectors lie in the plane: − 1 a + 1 b and − 1 a + 1 c .
h k h l
⎛ 1 1 ⎞ h k
K hkl ⋅ ⎜ − a + b⎟ = − a ⋅a + b ⋅b = −1+ 1 = 0
* *

⎝ h k ⎠ h k ∴K hkl ⊥ to both vectors

⎛ 1 1 ⎞ h k ∴K hkl ⊥ to the family of planes
K hkl ⋅ ⎜ − a + c⎟ = − a ⋅a * + c ⋅c* = −1+ 1 = 0
⎝ h l ⎠ h k

13 14

1 1
To Prove: dhkl = =
K hkl K hkl Diffraction
• Assume Khkl is the shortest RLV that points in the exact direction
• In handling scattering of x-rays (or electrons) by matter, we need
it points (i.e., h,k, and l have no common factor.) to characterize the x-ray beam by specifying its wavelength and
• Khkl is normal to the “hkl family of planes”. We can relate the direction of propagation:
distance between planes to the magnitude of Khkl: E = E0 x̂

lattice planes H = H 0 ŷ
k = kẑ
1 a K̂ hkl a b Ê0 × Ĥ0 = k̂
d hkl = a ⋅ K̂ hkl = cosθ a = cosθ a K hkl H = H0 exp {2π i(k ⋅r − ν t)}
h h h
Where K̂ hkl is a unit vector parallel to K hkl . Re H = H0 cos {2π (k ⋅r − ν t)} 1
K
Kˆhkl = hkl k =
K hkl E = E0 exp {2π i(k ⋅r − ν t)} λ
K ha + kb + lc
* * *
now, K̂ hkl = hkl = θb
θa a - a unit vector ReE = E0 cos {2π (k ⋅r − ν t)}
K hkl K hkl (0,1/k,0)
• Note: The usual physics definition is
so d hkl =
1
hK hkl
(
a ⋅ ha * + kb* + lc* ) (1/h,0,0)
dhkl = (1/h)a•Kˆhkl = (1/h) a Kˆ cosθa
k =
2π
dhkl = (1/k)b•Kˆhkl = (1/k) b Kˆ cosθb λ
1
∴ d hkl =
K hkl

15 16
 Additional Comments Traveling wave packet
• By “adding” up a narrow range of frequencies,
• In order to speak of the localization of an electron (or photon),
we must ‘blur’ the specification of the electron’s (photon’s) a “wave packet” can be constructed and a
wavelength, and allow that there is some uncertainty in the photon visualized.
wavelength (and frequency and energy):

E0 ( k ′ )exp {2π i( k ′z − ν t)} dk ′

∞
Ek (z,t) = ∫
−∞

where we have assumed, for simplicity, that the wave is

propagating along the z-axis and E0(k) is a function strongly
peaked near a particular ‘approximate’ wavenumber k.
• Electrons and photons are different in that wave packets for
electrons spread out over time, while photon wave packets
retain their width as they propagate. For more details, see:

http://farside.ph.utexas.edu/teaching/qmech/lectures/node1.html

http://farside.ph.utexas.edu/teaching/qmech/lectures/node1.html

17 18

Interference - “Time Lapse” pictures

Elastic Scattering
• When an x-ray is scattered by an atom it may emerge
in any direction, but unless absorption occurs, it has
the same wavelength:
1
k = k′ =
λ
• X-ray diffraction for structure determination is
concerned with interference effects that result from
scattering by periodic arrays of atoms.

This is my own heuristic

exercise, not “reality”.

19 20
 Atomic Form Atomic X-ray Atomic Form Factors: f (2θ)
scattering
Factors: f(2θ) • Forward scattering is more intense in “real
atoms” with diffuse electron clouds. If all the
electron density were concentrated very close to
the nucleus, 2θ dependence would disappear.
• f (2θ = 0) = N (number of electrons)

water ripples

• The “water ripples” concept is

not actually accurate; forward Atomic X-ray
scattering is actually more scattering
intense.
Clegg, p. 24.

21 22

“Thermal” effects: f ′(2θ) Interference between scatterers

• Vibrational motion “spreads out” average electron Consider the interference between two scatterers, separated by a
density and causes effective scattering at higher vector d:
1 k
2
angles to fall off more rapidly; U is the isotropic
displacement parameter (units of Å2 ).
20
⎛ −8π 2U sin 2 θ ⎞ k d

f j ′ (2θ ) = f j (2θ ) • exp ⎜

d

Cl– ⎟ k̂ =
15
⎝ λ2 ⎠ k
k′
kˆ ′ = 3 4
k′ k
10
f j (2θ ) Again, scattering at higher angles
1
is attenuated by spreading out the k = k′ =
λ
or k̂ = λ k

5 f j ′ (2θ ) electron density d

k′
d

0.2 0.4 0.6 0.8

sinθ/λ (Å–1 )
Clegg, p. 24.

23 24
 Interference between
Interference between scatterers scatterers
Consider the interference between two scatterers, separated by a • Amplitude of scattered wave
vector d:
∝ f1 (2θ ) + f 2 (2θ ) ⋅( phase shift factor)
k
k̂ = • The phase shift factor depends on the
k
path length difference =
k′
kˆ ′ =
k′ k̂ ⋅d + (−kˆ ′ ) ⋅d = (k̂ − kˆ ′ ) ⋅d
1
k = k′ = or k̂ = λ k
λ • For completely constructive
interference, where n is some integer:

(k̂ − kˆ ′ ) ⋅d = nλ or (k − k ′ ) i d = n

• For completely destructive interference

1
Clegg, Sec. 1-6. (k − k ′ ) i d = n +
2

25 26

• In a crystal, all pairs of translationally equivalent

• For the general case the amplitude of the
scattered wave:
A ∝ f1 (2θ ) + f 2 (2θ )cos ⎡⎣ 2π (k − k ′ ) • d ⎤⎦
cos ⎡⎣ 2π (k − k ′ ) • d ⎤⎦ = 1 when (k − k ′ ) • d = n
1
cos ⎡⎣ 2π (k − k ′ ) • d ⎤⎦ = −1 when (k − k ′ ) • d = n +
2
• In general we use a complex form:
A ∝ f1 (2θ ) + f 2 (2θ )exp {2π i(k − k ′ ) • d}
atoms are separated by some direct Lattice
Vector (Ri).
∴ If all atoms in the crystal that are related by
translational symmetry are to scatter X-rays to
give constructive interference simultaneously,
we must have the following:
Ri •(k – k′) = n or e2πi(k – k′)•R = 1

where Ri is any DLV.

27 28
 The beam is diffracted by a RLV! Bragg View
This places conditions on the possible
vectors k – k′ that are exactly the
same as the conditions used to define
RLVs. We therefore obtain the Laue
condition for diffraction:
k – k′ = Kj where Kj is some RLV
k

k´

k
K hkl

Clegg, Secs. 1.4-1.5.

29 30

Optical Transforms; Fraunhofer

Diffraction
Bragg

View • The diffraction phenomenon can
demonstrated with monochromatic visible
light by use of optical transforms.
• The phenomenon relies on interference
effects, like X-ray diffraction, though the
scattering mechanism is different.
• The interference phenomenon occurs when
the spacing between scatterers is on the
same order of magnitude as the wavelength
of the light used.

31 32
33 34

35 36
 Ewald Construction
• Start with reciprocal lattice
and the incident wavevector,
k, originating at (h,k,l) =
(0,0,0).
• Draw a sphere with the tip of
k at the center that contains
k
the origin, (0,0,0), on the
k′
(0,0,0) sphere’s surface.
K hkl
• As the direction of k is
K hkl = k – k′ changed, other RLVs (Kj’s)
move through the surface –
which is the condition that a
diffraction peak is observed.
Stout & Jensen, Sec. 2.4.

37 38

k k
Ewald Construction Limitations on the Data
k
k • Reflections (Kj’s) lie on the
Ewald sphere to meet the the
(0,0,l) diffraction condition.
• As the relative orientation of
c k′ k′ k′ the crystal and the incident X-
ray beam are varied, the
direction (but not the length)
a kk (0,0,0)
k1
of k changes, and k can in
kk principal point any direction.
k2
• Therefore, the “full sphere” of
possible reflections has radius
2|k| = 2k = 2/λ. The spacings
between the RLVs (RL points)
k′ k′
∝ 1/a (or 1/b or 1/c).
(h,0,0)
k′

39 40
 Getting more Data -
shorter λ
• Reflections (Kj’s) are limited to
those RLVs no further from the
origin than 2|k| = 2k = 2/λ.
• The spacings between the RLVs
(∝ 1/a or 1/b or 1/c) are
determined by the unit cell
dimensions.
kMo • For example, if the X-ray
kCu
(0,0,0)
wavelength is shortened, more
reflections fall “in the
sphere” (e.g., λCu = 1.54056
(Kα1), λMo = 0.71073 (Kα1).
k − k′ = K j ⇒ − k′ = K j − k
Use to get
⇒ k ′ i k ′ = (K j − k) i (K j − k) Laue equations
k 2 = K 2j − 2k i K j + k ′ 2
∴2k i K j = K j 2
2 2
2k K j cos(π 2 − θ ) = K j ⇒ 2k sin θ = K j ⇒ sin θ = K j
!# #"## $ λ
sin(θ )
2 2
⇒ sin θ = λ ⇒ sin θ = λ ⇒ 2d hkl sin θ = nλ Bragg's Law
n K hkl
Kj
In the last line we've used the fact that K j is a multiple of K hkl , which is the
shortest RLV for which h, k, and l have no common factors.
i.e., K j = nK hkl , where n = integer.

Stout & Jensen, Sec. 2.4.

41 42

Laue Equations
nλ = 2d hkl sin θ ;
Laue Equations, cont.
2
K hkl = (4 λ 2 )sin 2 θ where K hkl = ha * + kb* + lc* (***) Monoclinic 2
K hkl = (4 λ 2 )sin 2 θ
2 2 2 2 2 sin2 θ = Ah2 + Bk 2 + Cl 2 − Dhl
or [1 d ] = (4 λ )sin θ , since K hkl = [1 d ] where K hkl = ha * + kb* + lc* (***)
A = λ 2 (4a 2 sin2 β ); B = λ 2 4b2 ;
The “Laue Equations” for each crystal class can be derived from the form (***).
C = λ 2 (4c 2 sin 2 β ); D = ( λ 2 cos β ) (2acsin 2 β )
Cubic
or [1 d 2 ] = h2 (a 2 sin 2 β ) + k 2 b2 + l 2 (c 2 sin 2 β ) − 2hl cos β (ac sin 2 β )
sin2 θ = A(h2 + k 2 + l 2 ); A = λ 2 4a 2 or [1 d 2 ] = (h2 + k 2 + l 2 ) a 2
Triclinic
Tetragonal
sin2 θ = ( λ 2 4)[1 d 2 ]
sin2 θ = A(h2 + k 2 ) + Cl 2 ; A = λ 2 4a 2 ; C = λ 2 4c 2
h h h
or [1 d 2 ] = (h2 + k 2 ) a 2 + l 2 c 2 cos γ cos β 1 cos β 1 1
a a a
Hexagonal h k k k k k
1 cos α + cos γ cos α + cos α 1
sin2 θ = A(h2 + hk + k 2 ) + Cl 2 ; A = λ 2 3a 2 ; C = λ 2 4c 2 a b b b b b
l l l
or [1 d 2 ] = 4(h 2 + k 2 ) 3a 2 + l 2 c 2 cos α 1 cos β 1 cos β cos α
1 c c c
Orthorhombic =
d2 1 cos α cos β
sin2 θ = Ah2 + Bk 2 + Cl 2 ; A = λ 2 4a 2 ; B = λ 2 4b2 ; C = λ 2 4c 2
2 2 2 2 2 2 2
cos α 1 cos α
or [1 d ] = h a + k b +l c
cos β cos α 1

43 44
 Example Results
• The distances between lattice planes are on
If a hexagonal crystal has a (1 10) reflection the order of lengths of unit cells (~10 Å)
at 2θ = 8.5˚, at what 2θ angle would you • 50 Å ≥ dhkl ≥ 0.5 Å for most “small molecule
expect to observe the (110) reflection? structures”
• Two most common sources:
λCu = 1.540562 Å (Kα1)
λMo = 0.71073 Å (Kα1)

45

45 46

Neutron Diffraction Electron Diffraction

• In neutron diffraction, so-called thermal neutrons are • In high-energy electron
usually used. diffraction, electrons with 100
• Thermal neutrons have deBroglie wavelengths that are keV kinetic energies are
commonly used
comparable to typical X-ray wavelengths:
• e–’s have short deBroglie
λCu = 1.5418 Å, wavelengths:
λMo = 0.71069 Å, λCu = 1.5418 Å,
λn = h/pn = h[3mnkBT]-1/2 = 1.45 Å λMo = 0.71069 Å,
λe,100keV = h/p = h[2meE]-1/2 = 0.0039 Å
• A major advantage of neutron diffraction is in the very
different form factors, which have magnitudes that do • Ewald sphere is very large in
not scale with atomic number (good for many light comparison with reciprocal
lattice spacings. Therefore, a
atoms, especially deuterium). large section of any plane tangent
• Neutron spin (magnetic moment) can be exploited to to the Ewald sphere is effectively
probe magnetic ordering. “on the sphere” at the same time.

47 48
 Summary Multiple Atom Structures
• The geometrical aspects of a crystal (cell • Within translationally related sets of
atoms, the conditions for
dimensions, translational symmetry, etc.) constructive interference will be
determine the direct lattice. B B B satisfied simultaneously. However,
different sets of atoms will generally
• The direct lattice, in turn, determines the A A A
diffract the X-ray with different
phases.
reciprocal lattice. d d

• Example: For the “crystal” shown

• There is a one-to-one correspondence B B
here, when the set of A atoms all
scatter the X-ray constructively
between the RLVs and the vectors through A A A
with respect to each other, the set
d d d
which the incident radiation is diffracted. of B atoms will also scatter the X-
B B B ray constructively. But the the sets
• The geometry of the diffraction pattern is A A A
{Ai} and {Bi} will generally scatter
determined by the cell dimensions and d d d
with different phases.
• The resultant diffraction intensities
symmetry - no specific structural details will be determined by the sum of
B B B
beyond symmetry and dimensions of the unit the diffraction amplitudes due to
A A A {Ai} and {Bi} - including the effect of
cell affect the “positions” of diffraction peaks. different phases!

49 50

How do data determine “Structures” ? Structure Factors

• The positions of diffraction peaks tell us only
about the lattice parameters.
• The intensities of the peaks tell us about the
nature and positions of the atoms within the
unit cell.
• With n atoms distributed throughout the unit cell,
with fixed positions with respect to each other,
scatter X-rays that produce interference patterns.
Amplitude of scattered wave =

{ }
n
• The central problem of crystallography is in A ∝ SK = ∑ f j′ (K) exp 2π iK i d j
working backwards from the peak intensities j=1 !"# !##"## $
to locations and identities of atoms in the unit geometric factor
cell.
atomic form factor
Easier: How do “Structures” determine data? (determined by charge
distribution of the jth atom)

51 52
 The Structure Factor expression Recall: BCC treated as Primitive
& Systematic Absences (a/2)(–x^ + y^ + ^z)

a
• Symmetry operations place restrictions on a=
2
( x̂ + ŷ − ẑ ) az^

a
how atoms in the cell must be distributed. b = ( − x̂ + ŷ + ẑ ) a
2 b
(Physically, perhaps it is the other way a
c
c = ( x̂ − ŷ + ẑ )
around!) 2 (a/2)(x^ – y^ + ^z)

{ }
n ay^
A ∝ SK = ∑ f j ′ (2θ ) × exp 2π iK i d j Use to find Recip. Lattice Basis: ax^
j=1 !"
# # $ !##"##$
form factor geometric factor (a/2)(x^ + y^ – ^z)
b×c c×a a×b
• This means that there are symmetry a* =
V
; b* =
V
; c* =
V
a

relationships between the list of fj’s and dj’s. V = (a × b) • c

53 54

BCC treated with conventional cell (2 atoms/cell) • All recip. Lattice vectors are of the form
K hkl = ha ∗ + kb∗ + lc∗
a = ax̂ ⎫
⎪ x̂ ŷ ẑ ⎡ ⎧ ⎛ h k l ⎞ ⎫⎤
b = aŷ ⎬ ⇒ a* = ; b* = ; c* = S hkl = f Mo × ⎢exp {2π i(h i 0 + k i 0 + l i 0} + exp ⎨2π i ⎜ + + ⎟ ⎬ ⎥
a a a ⎝ 2 2 2 ⎠ ⎭ ⎥⎦
c = aẑ ⎪⎭ (a/2)(–x^ + y^ + ^z) ⎢⎣ ⎩

az^
{ }
S hkl = f Mo × ⎡⎣1+ exp π i ( h + k + l ) ⎤⎦
Atomic Positions: (a/2)(x^ + y^ + ^z)
d1 = 0 If h + k + l =
d 2 = 12 (a + b + c) c b a
{ }
even no. : exp iπ (h + k + l) = 1 ⇒ S hkl = 2 f Mo
exp {iπ (h + k + l)} = −1
Form Factors:
^ – y^ + ^z) odd no. : ⇒ S hkl = 0
f1′ (2θ ) = f 2′ (2θ ) = f Mo
(a/2)(x
′ ^
ay
^
ax
∴ if h + k + l = odd, reflection will not be observed.
^ + ^y – ^z)
(a/2)(x
a

55 56
 Recall: BCC treated as Primitive
^ ^
(1/a)(y + z)
Example: NaCl ⎧d Na1 = 0
⎪
1 ⎪d Na2 = 2 (a + b)
1
( , ,0)
1 1

a* = ( x̂ + ŷ )
2 2

a (1/a)z^
Na: ⎨
⎪d Na3 = 2 (a + c)
1
( ,0, )
1
2
1
2
1
b* = ( ŷ + ẑ )
⎪d = 1 (b + c)
⎩ Na4 2 (0, , )
1 1
2 2
a b*
1 (1/a)(x^ + z)
^
c* = ( x̂ + ẑ )
c* 1/a
a (1/a)y^
(1/a)x^
a*
⎧Cl1
⎪
( ,0,0)
1
2

⎪Cl2
Cl: ⎨
(0, ,0) 1
2
^ + y)
(1/a)(x ^
⎪Cl3 (0,0, )1
2
If we use the conventional cell (which leaves out half the lattice ⎪Cl4
⎩ (,,)1 1 1
2 2 2
points, the reciprocal lattice includes the ‘open’ points too:
x̂ ŷ ẑ
a = ax̂ ; b = aŷ ; c = aẑ ⇒ a* = ; b* = ; c* =
a a a
57 58

K hkl • ( 0,0,0 ) K hkl • ( 1 1

, ,0
2 2 ) K hkl • ( 1
2
,0, 12 ) (
K hkl • 0, 12 , 12 )
Systematic extinctions
due to face centering
⎡ ⎧ ⎛ h k⎞⎫ ⎧ ⎛ h l ⎞⎫ ⎧ ⎛ k l ⎞ ⎫⎤ h k l
S hkl = f Na ⎢1+ exp ⎨2π i ⎜ + ⎟ ⎬ + exp ⎨2π i ⎜ + ⎟ ⎬ + exp ⎨2π i ⎜ + ⎟ ⎬ ⎥
⎢⎣ ⎩ ⎝ 2 2⎠ ⎭ ⎩ ⎝ 2 2⎠ ⎭ ⎩ ⎝ 2 2 ⎠ ⎭ ⎥⎦ even even even S hkl = f Na i 4 + fCl i 4 = 4 f Na + fCl ( )
⎡ ⎧ ⎛ h⎞ ⎫ ⎧ ⎛ k⎞⎫ ⎧ ⎛ l ⎞⎫ Cl4 ⎤ odd odd odd S hkl = f Na i 4 + fCl i ( −4 ) = 4 f Na − fCl ( )
⎢exp ⎨2π i ⎜ ⎟ ⎬ + exp ⎨2π i ⎜ ⎟ ⎬ + exp ⎨2π i ⎜ ⎟ ⎬ ⎥
⎩ ⎝ 2⎠ ⎭ ⎩ ⎝ 2⎠ ⎭ ⎩ ⎝ 2⎠ ⎭ S hkl = f Na i 0 + fCl i 0 = 0
+ fCl ⎢ ⎥ odd even even
⎢ ⎧ ⎛ h k l ⎞ ⎫⎥
⎢ Cl1 Cl2 Cl3 + exp ⎨2π i ⎜ + + ⎟ ⎬ ⎥ even odd even S hkl = 0 (0,0,2)
⎢⎣ 1 ⎩ ⎝ 2 2 2 ⎠ ⎭ ⎥⎦ (0,2,2)

2(,0,0 ) 0, 12 ,0 ( )
0,0, 12 ( )
1 1 1
, . ( ) even even odd S hkl = 0
2 2 2 (2,2,2)

S hkl = 0
{ } {
S hkl = f Na ⎡⎣1+ exp π i ( h + k ) + exp π i ( h + l ) + exp π i ( k + l ) ⎤⎦ } { } odd odd even (1,1,1)

{ } { } { } { }
c*
+ fCl ⎡⎣exp π i ( h ) + exp π i ( k ) + exp π i ( l ) + exp π i ( h + k + l ) ⎤⎦ odd even odd S hkl = 0
a* b*
(0,2,0)
= f Na ⎡⎣1+ (−1) h+k
+ (−1) h+l
+ (−1) k+l ⎤ ⎡ h
⎦ + fCl ⎣(−1) + (−1) + (−1) + (−1)
k l h+k+l ⎤
⎦ even odd odd S hkl = 0 (2,0,0)
(2,2,0)

59 60
 Other systematic absences Consider h = k = 0

• Example: Systematic absences expected for … and l = odd

⎛ ⎞
a crystal with a 41 screw axis.
41 screw axis along c
{ }
S hkl ∝ ⎜ ∑ f p ⎟ exp ( 2π ilz ) i ⎡⎣1+ eπ i 2 + eπ i + e3π i 2 ⎤⎦ = 0
⎝ p ⎠
4 4 4 1st 2nd 3rd 4th
x, y, z ⎯⎯
1
→ y, x, z + 1
4 ⎯⎯
1
→ x , y, z + 1
2 ⎯⎯
1
→ y, x , z + 3
4 term term term term
(Every atom belongs to set of 4 symmetry-related atoms.) … and l = 2, 6, 10 …

{
⎧exp 2π i ( hx + ky + lz ) }
⎫ ⎛ ⎞
⎪ ⎪ { }
S hkl ∝ ⎜ ∑ f p ⎟ exp ( 2π ilz ) i ⎡⎣1+ eπ i + 1+ eπ i ⎤⎦ = 0
S hkl ∝ ∑ fp ⎨
{
⎪⎪+ exp 2π i ( −hy + kx + lz ) i e ( π i 2 )l
⎪⎪ } ⎝ p ⎠ (-1) (-1)
(π i )l ⎬
p {
⎪+ exp 2π i ( −hx − ky + lz ) i e ⎪ } … and l = 4, 8, 12 …
⎪ (3π i 2)l ⎪
{
⎪⎩+ exp 2π i ( hy − kx + lz ) i e ⎪⎭ } S hkl ∝ ∼ ⎡⎣1+ 1+ 1+ 1⎤⎦ (non zero)
(p refers to summation over the sets of symmetry-related atoms.) For h = k = 0, only reflections with l = 4, 8, 12 … will be observed.

61 62

Other systematic absences Symmetry of the Diffraction Pattern;

• Example: crystal with an a-glide ⊥ to a 41 axis. Equivalent Reflections - Laue Symmetry
(41 screw axis along c, ∴ a glide || to the ab-plane)
a−glide a−glide The pattern of single crystal diffraction “spots” is often
x, y, z ⎯⎯⎯⎯ → x + 1 2 , y, z ⎯⎯⎯⎯ → x + 1, y, z referred to as the intensity-weighted reciprocal space.

S hkl ∝ ∑ f p ⎨
{
⎧⎪exp 2π i ( hx + ky + lz ) ⎫
⎪ } Including the intensities, what symmetries should the
intensity-weighted reciprocal space exhibit?
p
⎩⎪ { (
+ exp 2π i h ( x + 1 2 ) + ky − lz ⎪
⎬
⎭
)} – In the absence of absorption and/or “anomalous scattering”,
reflections related to each other by inversion in reciprocal space,
(h,k,l) and (-h,-k,-l), should be of equal intensity. This is called
This will be zero when the term in brackets is zero: Friedel’s Law and it applies even for noncentrosymmetric space
{ } { (
exp 2π i ( hx + ky + lz ) = − exp 2π i h ( x + 1 2 ) + ky − lz )} groups (no inversion center).
The Patterson symmetry adds an inversion center if the
{ } {
exp 2π i ( lz ) = − exp 2π i ( h 2 − lz ) = −e } π ih
{
exp 2π i ( −lz ) } space group is acentric. Therefore, in centrosymmetric
exp {2π ilz } = −(−1) h exp {−2π ilz } cases, the Patterson symmetry is the same as the
symmetry of the diffraction pattern.
If l = 0,then absences occur where h = odd.
For b-glide ⊥ to c-axis, find absences where k = odd (l = 0).

63 64
 Symmetry of the Diffraction Pattern; Tl(1+x)BaSrCa(1–x)Cu2O(7-δ) Superconductor
Equivalent Reflections - Laue Symmetry
Translation of a crystal leaves reciprocal space • Within the disorder
model (x = 0.22), the
unaffected. Therefore, the translational parts of space group is
symmetry operations can be ignored in finding symmorphic: P4/mmm.
reflections that are expected to be equivalent. • The reciprocal lattice
– Screw operations have same symmetry effect as intensities reflect each
simple rotational point group operations symmetry operation
– Glide operations have the same symmetry effect as • No systematic
simple mirror planes absences

See: Table 11.4, p. 382 in Cotton. a = 3.8234 Å; c = 12.384 Å

65 66

Tl(1+x)BaSrCa(1-x)Cu2O(7-δ) Superconductor Tl(1+x)BaSrCa(1-x)Cu2O(7-δ) Superconductor

• Simulated electron
• Simulated electron diffraction pattern
diffraction • 100 plane.
• 001 plane. • The reciprocal
• The reciprocal lattice lattice intensities
intensities reflect reflect each
each symmetry symmetry
operation operation
• No systematic • No systematic
absences absences

67 68
Tl(1+x)BaSrCa(1-x)Cu2O(7-δ) Superconductor
Cs-Leucite, low symmetry (298K)
• Simulated electron
diffraction pattern • At high temp (473K),
• 110 plane. Cs-leucite
• The reciprocal (CsAlSi2O6) adopts a
lattice intensities cubic structure
reflect each (space group: Ia 3d ),
symmetry a = 13.7062Å.
operation • At room temperature,
• No systematic the symmetry is
absences lower
4
• What is it? I a1 3d2

69 70

Leucite (298K), l = 0 plane Leucite (298K), h = 0 plane

• Simulated electron • What symmetries are
diffraction pattern suggested?
• What symmetries
are possible?

71 72
 Leucite (298K), l = 0 plane Leucite (298K), l = 0 plane
• Adjacent spots have • Intense peaks are
a separation of indexed. (How was
0.153 Å–1. this done?)
• 1/(0.153 Å–1) = 6.536 Å.
What does this
number mean?

73 74

Powder Diffraction NaCl: h = 0 and h = k planes

• In principle, powder diffraction is nothing
more than a ‘spatially averaged’ version of
single-crystal diffraction.
• Much of the rich spatial information one
gathers in single-crystal data is lost in
powder diffraction, only the 2θ information
remains.
• However, once (if) the cell can be inferred, • The circles correspond to reflections on the
powder diffraction data is still quite same “cone”, i.e., with the same 2θ values.
powerful.

75 76
 • Any RLV is written as K hkl = ha ∗ + kb∗ + lc∗
Laue Equations
K hkl i K hkl = h2a ∗ i a ∗ + k 2b∗ i b∗ + l 2c∗ i c∗
• These are relations connecting observed 2θ
values and indices: 4
∗ ∗ ∗
+ 2hka ∗ i b∗ + 2hla ∗ i c∗ + 2klb∗ i c∗ = 2
sin 2 θ
Recall: a i a = b i b = c i c = 1 λ
a ∗ i b = a ∗ i c = b∗ i a = b∗ i c = c ∗ i a = c ∗ i b = 0
• Special cases:
earlier we found
Orthorhombic
2 4 1 1 1
K hkl = sin θ K hkl i K hkl = 2 sin 2 θ a∗ =
x̂ ; b∗ = ŷ ; c∗ = ẑ
λ λ a b c
2
or h2 k2 l2 ⎛ λ ⎞ ⎛ h2 k 2 l 2 ⎞
K2 = + + ⇒ sin 2 θ = ⎜ ⎟ ⎜ 2 + 2 + 2 ⎟
2 a2 b2 c2 ⎝ 2⎠ ⎝ a b c ⎠
λ 2 ⎛ λ ⎞
sin 2 θ = 2
K hkl =⎜ ⎟
4 ⎝ 2d hkl ⎠

77 78

• Reciprocal lattice
• Cubic and Tetragonal - special cases of
orthorhombic: 2 b×c acx̂ 2
⎛ λ⎞ a∗ = = = x̂
sin θ = ⎜ ⎟ (h2 + k 2 + l 2 ) cubic
( )
2
⎝ 2a ⎠
V 3 2 a 2c 3a
⎛h +k 2
l ⎞
2 2
sin 2 θ = λ 2 ⎜ + 1 ⎛ x̂ ⎞ 1
⎟ tetragonal b∗ = + ŷ ; c∗ = ẑ
⎝ 4a
2
4c 2 ⎠ ⎜
a⎝ 3 ⎟
⎠ c
• Hexagonal
c out of plane of paper • Laue equation
α = β = 90° γ = 120° 3 1 λ2 λ2 ⎡ 2 ∗ 2 2 ∗ 2 2 ∗ 2 ⎤
a = a( x̂ − ŷ)
2
sin θ = K iK = ⎢ h a + k b + l c + 2hka ∗ i b∗ ⎥
2 2 4 4 ⎣ ⎦
b = aŷ
c = cẑ sin 2 θ =
λ2 2 2
3a 2
h(+ k + hk +
λ2 2
4c 2
l )
3 2
V = a i (b × c) = a c
2
79 80