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PG/KA/Chap 3 - 1

Chap 3. Light-Matter Interaction


Electromagnetic wave [SR 5.2] (outline)
1. Maxwell Eq with vector (A) and scalar () potentials
2. Vacuum (no charge, no current) = 0, i = 0, Coulomb gauge A = 0
3. Wave Eq :
1
c
2

2
A
t
2
=
2
A Plane wave A = A
0
cos(k r t)
4. (Energy from elds amplitude) = (Photon density)(Energy quantum)
A
0
= 2c(2 hN/V )
1/2
Minimal Electromagnetic Interaction (charged particles)
H =
1
2m
_
p
q
c
A
_
2
+q
_
classical eq of motion with
Lorenz force F = q(E +v B/c)
_
Using : p i h , A = 0 (Coulomb gauge)
H = H
0
+V, V =
q
mc
(A p) +
q
2
2mc
2
A A
(weak-eld approximation neglects the 2nd term [SR 5.3.3])
PG/KA/Chap 3 - 2
Absorption and Emission Spectra (1st order processes)
V =
q
mc
(A p) =
q
mc
A
0
cos(k r t) p
U(k)e
it
+U(k)e
it
_
U(k)
qA
0
2mc
e
ikr
p
_
(periodic interaction)

Fermis golden-rule : |m |k
w
km
=
2
h
|U
km
(k)|
2
(E
k
E
m
h) (Absorption)
+
2
h
|U
km
(k)|
2
(E
k
E
m
+ h) (Emission)
(Absorption or Emission sign of E
k
E
m
)
PG/KA/Chap 3 - 3
Dipole Approximation (long wavelength)
Visible lights (electronic transitions) :
=400 700 nm dimension of molecules
(even longer wavelength for infrared and microwave lights)
e
ikr
1 (|k| = 2/)
Then, U
km

qA
0
2mc
k[ p[m)
Using : p =
im
h
[H
0
, r]
_
[H
0
, r
i
] = [

I
P
2
I
2M
I
+

j
p
2
j
2m
+ V (r, R), r
i
]
=
1
2m
[p
2
i
, r
i
] =
h
im
p
i
_
U
km
=
qA
0
2mc
im
h
k[[H
0
, r][m) =
qA
0
2mc
im
h
k[r[m)(E
k
E
m
)
From the functions in w
km
, E
k
E
m
= h (+ : absorption, : emission)
U
km
=
iA
0

2c
k|qr|m transition dipole moment
PG/KA/Chap 3 - 4
So far, we have treated one particle (with charge q ).
By considering all nuclei and electrons in molecular systems,
V =
1
c
A (

I
Z
I
M
I
P
I

e
m

i
p
i
)
We arrive at (Note : all calculations were linear)
U
km
=
iA
0

2c
k[(

I
Z
I
R
I
e

i
r
i
)[m) =
iA
0

2c

km

km
: transition dipole of the molecular system
(Note : in [SR 5.4] only electrons are considered, but we should include nuclei to treat IR spectra
etc.)
Simpler derivation of U
km
[SR 5.5.2]
We get the same U
km
(more easily) starting from V = E with
E =
1
c
A
t
=

c
A
0
sin(k r t) =
A
0
2ic
(e
i(krt)
e
i(krt)
)
(Coulomb gauge = 0 )
PG/KA/Chap 3 - 5
Density of states of photon eld
Having specied the states ( |m |k ) of the molecular system, we still
need to sum over the photon eld states
w
abs/em
(m k) =
_
w
km

photon
( h)d( h)
Insert w
km
of page 2 :
w
abs
(m k) =
2
h
[U
km
(k)[
2

photon
(E
k
E
m
)
w
em
(m k) =
2
h
[U
km
(k)[
2

photon
(E
m
E
k
)
Calculation of
photon
( h)
1. Number of states N in wave vector k : dN = (
L
2
)
3
dk
_
Periodic boundary condition in length L :
e
ik
x
(x+L)
= e
ik
x
x
k
x
L = 2n
x
(n
x
= 0, 1, 2, )
_
2. Use polar coordinate dk = k
2
dkd and k = /c : dN =
V
(2)
3

2
c
3
dd
PG/KA/Chap 3 - 6
3. d
photon
( h) =
dN
d( h)
=
V
(2c)
3

2
h
d
_
(Dierential) density of photon
states having k directed to d
_
Thus, (dierential) emission rate toward d :
dw
em
(m k)
d
=
2
h
[U
km
[
2
d
photon
(E
k
E
m
)
d
=
N
3
2 hc
3
[
km
[
2
_
used |U
km
| = (A
0
/2c)|
km
|, A
0
= 2c(2 hN/V )
1/2
, h = E
k
E
m

[
km
[ = [
km
[ sin ( angle between k and
km
)
Integration over the solid angle d
__
dsin
2
=
_
2
0
d
_

0
sin d sin
2
=
8
3

Total emission rate


w
em
(m k) =
4N
3 h
_

c
_
3
[
km
[
2
However, it is not correct to have w
em
0 for N 0, since in
reality, we have spontaneous emissions.
To remedy this, we just need to replace N by N + 1, which is
indeed justied via quantization of radiation (photon) eld.
PG/KA/Chap 3 - 7
_

_
Quantization of radiation eld : Photon state |n =
1

n!
(b

)
n
|0
n 1|b|n =

n n + 1|b

|n =

n + 1
(absorption) (emission)
1|b

|0 = 1 = 0 spontaneous emission into the photon vacuum is possible.


(On the other hand, we have no spontaneous absorption since b|0 = 0 )
_

_
Natural lifetime of excited states of an excited state [m)
summing over all |k in lower energy E
k
< E
m
:
1

rad
(E
m
)
=

E
k
<E
m
w
em
(m k)[
N=0
=

E
k
<E
m
4
3 h
_
[
km
[
c
_
3
[
km
[
2
Rate of photo-absorption (Similarly to the emission case)
w
abs
(m k) =
4
3 h
N
_

c
_
3
|
km
|
2
[w
abs
0 as N 0 : no spontaneous absorption ]
PG/KA/Chap 3 - 8
Miscellaneous
Einsteins A and B factors [SR 5.4.6]
Photon eld density of states (or energy)
SR uses that for quantized plane-wave (temperature independent)
Many others use black-body Planck distribution (temperature dependent)
or discuss without explicit form of the density of states.
(Indeed, the A, B factors are dened from the photon-eld independent part of
the transition rate.)
Oscillator strength
f
km

2m
3 he
2
[
km
[
2
(dimensionless)
Dened as relative intensity to
n = 0 1 transition of 3D harmonic oscillator (which gives f = 1 ... (*)).
_
Exercise : Derive (*) via the following two routes:
1. Using creation-annihilation operator
2. Carrying out Gaussian integration of the wavefunctions representation
_
PG/KA/Chap 3 - 9
_

_
Answer : (3D H.O. H =
1
2m
p
2
+
m
2
2
|x|
2
, m/ h )
1. b = (m/2 h)
1/2
(x+ip/m), b

= (m/2 h)
1/2
(xip/m) x = (m/2 h)
1/2
(b+b

)/2
Using b|n =

n|n 1, b

|n =
_
n + 1|n + 1 1|x|0 = ( h/2m)
1/2
Thus, |1|er|0|
2
= 3
he
2
2m
(where 3 from x, y, z components)
2.
0
= (/)
1/4
exp(x
2
/2),
1
=

2(/)
1/4
x exp(x
2
/2)

_
dx
0
x
1
=
_
2/
_
dxx
2
e
x
2
=
_

_
Correspondence with experiments
Beer-Lambert Law : I
l
= I
0
e
Cl
_
... absorption coecient
C ... molar concentration
_
Integrated absorbance ,
_
()d
Considering the decay of photon eld energy, we get (skipping details)
, =
h
km
c
LB =
4
2

km
L
3 hc
[
km
[
2
B ... Einsteins B-coe.
L ... Avogadro number

km
... central peak frequency of the |m |k absorption band
(or in the derivation, representative when approximating
_
()

d
1

_
()d )
PG/KA/Chap 3 - 10
1st correction to long-wavelength approx. [SR 5.4.8]
Dipole Approx : e
ikr
1 ([k[ = 2/)
To 1st-order : e
ikr
= 1 +k r +
U
km
=
eA
0
2mc
k[e
ikr
p[m)

iA
0

km
2c

km
. .

i
2
A
0
(k )
. .
M
km
+
1
4e
A
0

km
c

. .
Q
km
k
(dipole approx.) H E
M =
e
2mc
(r p) ... magnetic dipole
Q
ij
= (er
i
)(er
j
) ... electric quadrupole tensor (r
i
= x, y, z)
Symmetry :
x, y, z , M R
x
, R
y
, R
z
, (rotation) Q xy, x
2
, etc.
dierent symmetry for each term
PG/KA/Chap 3 - 11
Franck-Condon Factor
Molecular wavefunction (adiabatic approx.)

,
(r, R)
,
(R)

(r; R)
_
Quantum number
... electronic
... nuclear
_
Transition dipole for (, ) (

) :

,
=
_
dR
_
dr

=
_
dR


_
dr

. .

(R)[

(R)
Expand around a (particular) nuclear conguration R
0
(usually minimum of the adiabatic potential)

(R) =

(R
0
) +
_

R
_
R=R
0
(R R
0
) +
PG/KA/Chap 3 - 12
Then,

,
=

(R
0
)

)
. .
+ (non-Condon terms)
(Franck-Condon factor)
_
In many cases, large Franck-Condon overlap at vertical transitions
Nuclei dont move during fast electronic transitions
(semi-classical interpretation)
_
.
.
.
.
.
.
.

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