Professional Documents
Culture Documents
E.g. Selenium
Courtesy of Michael R. Sawaya. Used with permission.
Anomalous Scattering
When the incident radiation has sufficient energy to promote an electronic
transition in atoms contained in the crystal, we observe anomalous
scattering in non-centrosymmetric crystals.
h=E
h<E
Excites a transition
from the K shell
For Se: = 0.9795
No transition possible,
Insufficient energy
usual case
E.g. Selenium
Anomalous Scattering
Anomalous scattering causes small but measurable differences in
intensity between the reflections hkl and -h-k-l not normally present. That
means for non-centrosymmetric crystals in the presence of atoms heavier
than sulfur, Friedels law is not strictly true.
Under normal conditions,
electron distributions within
atoms are centrosymmetric:
(-15,0,6)
(0,0,0)
I(hkl) = I(-h-k-l)
and
(hkl) = -(-h-k-l)
Courtesy of Michael R. Sawaya. Used with permission.
(15,0,-6)
Fh,k,l
(-h,-k,-l)
imaginary
,
|F h
F-h,-k,-l
imaginary
l
k,
hkl
real
-h-k-l
|F
I(hkl) = I(-h-k-l)
and
(hkl) = -(-h-k-l)
Courtesy of Michael R. Sawaya. Used with permission.
-h
,- k
,- l |
real
imaginary
I(hkl) = I(-h-k-l)
and
(hkl) = -(-h-k-l)
,
h
F
Fh,k,l
l
k,
hkl
-h-k-l
real
|F
-h
,- k
,- l |
F-h,-k,-l
Anomalous Scattering
Anomalous scattering causes small but measurable differences in
intensity between the reflections hkl and -h-k-l not normally present. That
means for non-centrosymmetric crystals in the presence of atoms heavier
than sulfur, Friedels law is not strictly true.
Under normal conditions,
electron distributions within
atoms are centrosymmetric:
e-
Anomalous Scattering
In the presence of anomalous scattering, F(hkl) and F(-h-k-l) obey neither
of the two relationships of Friedels Law and we are able to measure
the differences between F(hkl) and F(-h-k-l).
I(hkl) I(-h-k-l)
and
(hkl) -(-h-k-l)
How to calculate F for an anomalous scatterer?
The correction to the atomic scattering factor is derived
from classical physics and is based on an analogy of
the atom to a forced oscillator under resonance
conditions.
The housing of a
motor vibrating
due to periodic
impulses from an
irregularity in the
shaft.
e-
nucleus
Courtesy of Michael R. Sawaya. Used with permission.
e-
E=h
e-
nucleus
+
+
+
Incident
photon
with
= B
v Eo
e
A=
2
2
2
mc vB v + ikv
e+
m = mass of oscillator
e = charge of the oscillator
c = speed of light
Eo = max value of electric vector of incident photon
= frequency of external force (photon)
B = natural resonance frequency of oscillator (e-)
f=
nucleus
Amplitude of scattered radiation from the forced eAmplitude of scattered radiation by a free e-
Incident
photon
with
e-
Scattered
photon
= B
f = fo+ f + if
= frequency incident photon
B = Bohr frequency of oscillator (e-)
(corresponding to electronic transition)
fo
Normal
scattering
factor
REAL
v
vB
f ' = g loge 1
v
vB
correction
factor
REAL
Courtesy of Michael R. Sawaya. Used with permission.
f " = g
vB2
v2
correction
factor
IMAGINARY
f = fo+ f + if
2
v
vB
f ' = g log e 1
v
vB
f " = g
vB2
v2
when >B
Else, 0
>
f
= B
= B
f = fo+ f + if
real component, f
imaginary component, f
Maximum negative
force
Zero speed
Maximum positive
force
Zero speed
Zero force
Maximum +/- speed
Courtesy of Michael R. Sawaya. Used with permission.
Maximum negative
force
Zero speed
force : speed
incident photon : re-emitted photon.
Maximum positive
force
Zero speed
Zero force
Maximum +/- speed
time->
Imaginary axis
fo
fo
f
f
Real axis
real
Positive
number
real
180 out of phase
imaginary
90 out of phase
+ kyH + lzH )
Imaginary axis
fo
Real axis
FH(hkl)
Imaginary axis
Real axis
FH(-h-k-l)
FH(-H-K-L)
-
fo
f
f
Imaginary axis
fo
Real axis
H(hkl)
H(-h-k-l)
fo
f
f
H(hkl) H(-h-k-l)
Courtesy of Michael R. Sawaya. Used with permission.
FH(hkl)
FH(-h-k-l)
FH(hkl)
Real axis
H(hkl)
H(-h-k-l)
FH(-h-k-l)
IH(hkl) = IH(-h-k-l)
H(hkl) H(-h-k-l)
Courtesy of Michael R. Sawaya. Used with permission.
F(hkl)
FH(hkl)
FL(hkl)
Real axis
FL(-h-k-l)
FH(-h-k-l)
F(-h-k-l)
I(hkl) I(-h-k-l)
(hkl) (-h-k-l)
There is an observable
difference between
|F(-h-k-l)| and |F(hkl)| called
a Bijvoet or Friedel
difference or an
anomalous difference.
This difference is only
small (typically 1-3% of
the measured intensity)
and it is not always
trivial to determine it
accurately.
Anomalous Signal
Imaginary axis
F(hkl)
FH(hkl)
FL(hkl)
Real axis
FL(-h-k-l)
FH(-h-k-l)
F(-h-k-l)
F(hkl) F(-h-k-l)
Courtesy of Michael R. Sawaya. Used with permission.
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