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Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16

Solid State Physics

 
Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16
Solid State Physics 2. X-ray Diffraction 1 08/27/16
 
         

2. X-ray Diffraction

Solid State Physics 2. X-ray Diffraction 1 08/27/16
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Diffraction 2 08/27/16
Diffraction 2 08/27/16
Diffraction 2 08/27/16
Diffraction 2 08/27/16
Diffraction 2 08/27/16

Diffraction

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2
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Diffraction 2 08/27/16
m  W sin   Diffraction m  1 , 2 , 3 , ...
m  W sin   Diffraction m  1 , 2 , 3 , ...
m  W sin   Diffraction m  1 , 2 , 3 , ...
  • m

W

sin

Diffraction

m  W sin   Diffraction m  1 , 2 , 3 , ...
m  W sin   Diffraction m  1 , 2 , 3 , ...

m

1, 2,3, ...

m  W sin   Diffraction m  1 , 2 , 3 , ...
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Diffraction 4 08/27/16
Diffraction 4 08/27/16
Diffraction 4 08/27/16

Diffraction

Diffraction 4 08/27/16
Diffraction 4 08/27/16
Diffraction 4 08/27/16
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Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16
Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16

Diffraction using Light

Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16
Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16

One Slit

Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16

Two Slits

m sin  d
m
sin 
d

http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html

Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16
Diffraction using Light One Slit Two Slits m sin  d http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Diffdouble.html Diffraction Grating 5 08/27/16

Diffraction Grating

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5
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Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in
Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in
Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in

Diffraction

Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in
Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in
Diffraction The diffraction pattern formed by an opaque disk consists of a small bright spot in

The diffraction pattern formed by an opaque disk consists of a small bright spot in the center of the dark shadow, circular bright fringes within the shadow, and concentric bright and dark fringes surrounding the shadow.

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Photons Diffraction for Crystals Electrons Neutrons Diffraction techniques exploit the scattering of radiation from large numbers
Photons Diffraction for Crystals Electrons Neutrons Diffraction techniques exploit the scattering of radiation from large numbers
Photons Diffraction for Crystals Electrons Neutrons Diffraction techniques exploit the scattering of radiation from large numbers

Photons

Diffraction for Crystals

Electrons

Neutrons

Diffraction techniques exploit the scattering of radiation from large numbers of sites. We will concentrate on
Diffraction techniques exploit the
scattering of radiation from large
numbers of sites. We will concentrate
on scattering from atoms, groups of
atoms and molecules, mainly in
crystals.
There are various diffraction
techniques currently employed which
result in diffraction patterns. These
patterns are records of the diffracted
beams produced.
Photons Diffraction for Crystals Electrons Neutrons Diffraction techniques exploit the scattering of radiation from large numbers
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What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16

What is This Diffraction?

What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
What is This Diffraction? 8 08/27/16
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Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 
Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 
Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 

Bragg Law

Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 
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Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 
Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 

William Lawrence Bragg 1980 - 1971

2d sinn

08/27/16

Bragg Law 9 William Lawrence Bragg 1980 - 1971 2 d sin   n 
Mo Cu Co Cr 0.07 nm 0.15 nm 0.18 nm 0.23 nm 10
Mo
Cu
Co
Cr
0.07 nm
0.15 nm
0.18 nm
0.23 nm
10
Mo Cu Co Cr 0.07 nm 0.15 nm 0.18 nm 0.23 nm 10 08/27/16

08/27/16

Monochromatic Radiation 11 08/27/16
Monochromatic Radiation 11 08/27/16
Monochromatic Radiation 11 08/27/16
Monochromatic Radiation 11 08/27/16
Monochromatic Radiation 11 08/27/16

Monochromatic Radiation

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Monochromatic Radiation 11 08/27/16
Diffractometer 12 08/27/16
Diffractometer
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Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship
Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship
Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship

Nuts and Bolts

Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship
Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship

The Bragg law gives us something easy to use, To determine the relationship between diffraction

Angle and planar spacing (which we already know

Is related to the Miller indices).

But… We need a deeper analysis to determine the Scattering intensity from a basis of atoms.

Nuts and Bolts The Bragg law gives us something easy to use, To determine the relationship
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Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1
Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1
Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1

Reciprocal Lattices

Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1
Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1

Simple Cubic Lattice

a  axˆ a  ayˆ a  azˆ 1 2 3
a
 axˆ
a
 ayˆ
a
 azˆ
1
2
3
Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1

ur

G

1

2

a

ur

G

2

2

a

ur

G

3

2

a

Reciprocal Lattices  Simple Cubic Lattice a  axˆ a  ayˆ a  azˆ 1

The reciprocal lattice is itself a simple cubic lattice with lattice constant 2/a.

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Reciprocal Lattices  BCC Lattice 1 (  xˆ yˆ z)ˆ 1 yˆ z)ˆ a 
Reciprocal Lattices  BCC Lattice 1 (  xˆ yˆ z)ˆ 1 yˆ z)ˆ a 
Reciprocal Lattices  BCC Lattice 1 (  xˆ yˆ z)ˆ 1 yˆ z)ˆ a 

Reciprocal Lattices

BCC Lattice

   

1

 

(

 

 

z)ˆ

 

1

   

 

z)ˆ

 
     

a

a

 

a

a

(xˆ

 

 

1

2

 

2

2

 
 

1

a

(xˆ

z)ˆ

       
   
a 3  2   0  a 1  a 2  a 3
   

a

3

2

0

a

1

a

2

a

3

 

1

2

a

3

       
 
 
 
ur G

ur

G

1

2

ˆ

y

ˆ

z

ur

G

2

2

ˆ

x

ˆ

z

 

ur

G

3

2

ˆ

x

 

a

a

a

y ˆ
y ˆ

The reciprocal lattice is represented by the primitive vectors of an FCC lattice.

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Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a
Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a
Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a

Reciprocal Lattices

FCC Lattice

2  2  2  yˆ a a a
2
2
2
a
a
a

a

1

 

a

2

a

3

0

a  a 1
a
a
1

2

a 3
a
3

a

3

 
 
 

G

 

1

a

(

z)ˆ

 

G

 

1

a

(xˆ

z)ˆ

1

2

2

2

 

ur

 

G

 

1

a (xˆ

z)ˆ

 

3

2

Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a
Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a
Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a
Reciprocal Lattices  FCC Lattice 2  2  2  yˆ a a a a

The reciprocal lattice is represented by the primitive vectors of an BCC lattice.

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Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal

Drawing Brillouin Zones WignerSeitz cell

Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal

The BZ is the fundamental unit cell in the space defined by reciprocal lattice vectors.

Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
Drawing Brillouin Zones The BZ is the fundamental unit cell in the space defined by reciprocal
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Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16

Drawing Brillouin Zones

Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
Drawing Brillouin Zones 19 08/27/16
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Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The

Back to Diffraction

Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The

Diffraction is related to the electron density. Therefore, we have a ...

Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The

The set of reciprocal lattice vectors determines the possible x-ray reflections.

Back to Diffraction Diffraction is related to the electron density. Therefore, we have a ... The
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2  r sin  k r  k  r    (k 
2  r sin  k r  k  r    (k 
 

2

r

sin

k r

kr

   

   
 

(kk)r

 

The difference in path length of the of the incident wave at the

The difference in phase angle is

For the diffracted wave, the phase difference is

points O and r is

r sin
r sin

So, the total difference in phase angle is

2  r sin  k r  k  r    (k 
2  r sin  k r  k  r    (k 
2  r sin  k r  k  r    (k 
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Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional
Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional
Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional

Diffraction Conditions

Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional
Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional

Since the amplitude of the wave scattered from a volume element is proportional to the local electron density, the total amplitude in the direction k is

f

n

n

  • (r) k

e

i k

  • (r) k)

e

i (

r

r

dV

dV

 
     
 

k  k k

Diffraction Conditions  Since the amplitude of the wave scattered from a volume element is proportional
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Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we
Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we
Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we

Diffraction Conditions

Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we
Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we

When we introduce the Fourier components for the electron density as before, we get

r  i s (  k)  r f   n e dV s
r
i s
(

k)
r
f
 
n e
dV
s
s
r s   k
r
s
 k

Constructive

Interference

Diffraction Conditions  When we introduce the Fourier components for the electron density as before, we
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Diffraction Conditions k  k  k r s   k r 2 2 (k
Diffraction Conditions k  k  k r s   k r 2 2 (k
Diffraction Conditions k  k  k r s   k r 2 2 (k

Diffraction Conditions

k  k  k
k  k  k
Diffraction Conditions k  k  k r s   k r 2 2 (k
Diffraction Conditions k  k  k r s   k r 2 2 (k
r s   k r 2 2 (k  s )  k r 2
r
s
 k
r
2
2
(k
s
)
k
r
2
or
2 k 
s
s
Diffraction Conditions k  k  k r s   k r 2 2 (k
k  s  k 

ks k

Diffraction Conditions k  k  k r s   k r 2 2 (k

2d sinn

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Diffraction Conditions  For a crystal of N cells, we can write down r  
Diffraction Conditions  For a crystal of N cells, we can write down r  
Diffraction Conditions  For a crystal of N cells, we can write down r  

Diffraction Conditions

Diffraction Conditions  For a crystal of N cells, we can write down r  
Diffraction Conditions  For a crystal of N cells, we can write down r  

For a crystal of N cells, we can write down

 

r

 
 

 

i s

r

F N

cell

n

(r)

e

dV NS

s

 

s

 
 

n

(r)

n

j

(r

r )

j

 
j  1
j  1
Diffraction Conditions  For a crystal of N cells, we can write down r  
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Diffraction Conditions  The structure factor can now be written as integrals over s atoms of
Diffraction Conditions  The structure factor can now be written as integrals over s atoms of
Diffraction Conditions  The structure factor can now be written as integrals over s atoms of

Diffraction Conditions

Diffraction Conditions  The structure factor can now be written as integrals over s atoms of
Diffraction Conditions  The structure factor can now be written as integrals over s atoms of

The structure factor can now be written as integrals over s atoms of a cell.

 

r

 
 

 

j

 

i s

r

S

   

(r

r)

j

 

dV

s

cell

n

j

e

 

r

i s

r

j

 

r

i s

 

 

e

n

j

(

)

e

 

dV

 

j

 

r

 

f

j

n

j

(

)

e

i s

dV

Atomic form factor

Diffraction Conditions  The structure factor can now be written as integrals over s atoms of
Diffraction Conditions  The structure factor can now be written as integrals over s atoms of
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Diffraction Conditions  Let r  x a  y a  z a j 1
Diffraction Conditions  Let r  x a  y a  z a j 1
Diffraction Conditions  Let r  x a  y a  z a j 1

Diffraction Conditions

Diffraction Conditions  Let r  x a  y a  z a j 1
Diffraction Conditions  Let r  x a  y a  z a j 1

Let

r  x a  y a  z a j 1 2 3 j j
r  x
a
 y
a
 z
a
j
1
2
3
j
j
j

Then, for an given h k l reflection

r

r

r

r

 

r

r

r

s

r

j

(

h

hx

a1

j

k

a

2

l

ky lz

j

j

a3 )

 

(

x

j

a1

y

j

a

2

z

j

a 3 )

 
 

S

s

j

f e

j

i

2

hx ky lz

j

j

j

 
 
Diffraction Conditions  Let r  x a  y a  z a j 1
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Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,
Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,
Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,

Diffraction Conditions

For a BCC lattice, the basis has identical

Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,
Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,
( x y z , , )  (0,0,0) 1 1 1
(
x y z
,
,
)
(0,0,0)
1
1
1

atoms at

( x , y z , )  ( 1 , 1 , 1 ) 2
(
x
,
y z
,
)
(
1
,
1
,
1
)
2
2
2
2
2
2

The structure factor for this basis is

 i2   h k   l  S  f (1  e
i2
h k
l
S
f
(1
e
)
G

S is zero when the exponential is i×

(odd integer) and S = 2f even.

when h + k + l is

Diffraction Conditions  For a BCC lattice, the basis has identical ( x y z ,

So, the diffraction pattern will not contain lines for (100), (300), (111), or (221).

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Diffraction Conditions  For an FCC lattice, the basis has identical atoms at 000, 0 1
Diffraction Conditions  For an FCC lattice, the basis has identical atoms at 000, 0 1
Diffraction Conditions  For an FCC lattice, the basis has identical atoms at 000, 0 1

Diffraction Conditions

Diffraction Conditions  For an FCC lattice, the basis has identical atoms at 000, 0 1
Diffraction Conditions  For an FCC lattice, the basis has identical atoms at 000, 0 1

For an FCC lattice, the basis has identical atoms at

000, 0 1 1 , 1 0 1 , and 1 1 0 2 2 2
000, 0
1
1
,
1
0
1
, and
1
1
0
2
2
2
2
2
2

The structure factor for this basis is

S  G
S 
G
 i   k l    i   h  l 
i
k l
i
h
l
i
h k
f
(1
e
e
e
)
when hkl are all even
or all odd.

S = 4f

S = 0 when one of hkl is either even or odd.

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Structure Determination Simple a  d  Cubic 2 2 2 h  k  l
Structure Determination Simple a  d  Cubic 2 2 2 h  k  l
Structure Determination Simple a  d  Cubic 2 2 2 h  k  l

Structure Determination

Simple a  d  Cubic 2 2 2 h  k  l
Simple
a
d 
Cubic
2
2
2
h
k
l

When combined with the Bragg law:

sin

2

  • 4 a

2

h

2

k

2

l

2

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32
Structure Determination Simple a  d  Cubic 2 2 2 h  k  l

08/27/16

 X-ray powder pattern (degrees) sin 2  ratios hkl determined using Cu K 11.44 0.0394
 X-ray powder pattern (degrees) sin 2  ratios hkl determined using Cu K 11.44 0.0394
 X-ray powder pattern (degrees) sin 2  ratios hkl determined using Cu K 11.44 0.0394
 X-ray powder pattern (degrees) sin 2  ratios hkl determined using Cu K 11.44 0.0394
X-ray powder pattern
(degrees)
sin 2
ratios
hkl
determined using Cu K
11.44
0.0394 1
radiation,  = 1.542 Å
100
16.28
0.0786 2
110
20.13
0.1184 3
111
23.38
0.1575 4
200
26.33
0.1967 5
210
29.07
0.2361 6
211
34.14
0.3151 8
220
36.53
0.3543 9
300,
221
38.88
0.3940 10
310
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 X-ray powder pattern (degrees) sin 2  ratios hkl determined using Cu K 11.44 0.0394
Structure Determination (310) sin 2    4 a 2  h 2  k
Structure Determination (310) sin 2    4 a 2  h 2  k
Structure Determination (310) sin 2    4 a 2  h 2  k

Structure Determination (310)

Structure Determination (310) sin 2    4 a 2  h 2  k
Structure Determination (310) sin 2    4 a 2  h 2  k

sin

2

4

a

2

h

2

k

2

l

2

0.3940  

(1.5420)

2

  • 2

  • 4 a

    • 10

a

3.88 angstroms

Structure Determination (310) sin 2    4 a 2  h 2  k
Structure Determination (310) sin 2    4 a 2  h 2  k
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