Femtochemistry:

A theoretical overview
VI Transition probabilities

Mario Barbatti
mario.barbatti@univie.ac.at
This lecture can be downloaded at
http://homepage.univie.ac.at/mario.barbatti/fem
tochem.html

Fermis golden rule

Fermis Golden Rule

Transition rate:

2
2
Wk
i H p k k

k , k

Quantum levels of
the non-perturbed
system

Perturbation is
applied

i
Transition is
induced

Derivation of Fermis Golden Rule

See Fermis Golden Rule paper at the course homepage

Time-dependent formulation

H 0
t

H H0 H p

H0 Non-perturbated Hamiltonian
Hp Perturbation Hamiltonian

H 0 En n 0

which solves:

i j ij

and

Ei E j ij
4

Derivation of Fermis Golden Rule

an t e iEnt n
n

H H0 H p
i H 0

Multiply by

at left and integrate

Prove it!

ak t
k H p n an t eiknt
t
n

Note that the non-perturbated Hamiltonian is supposed non-depen

5

An approximate way to solve the differential equation

ak t
k H p n an t e iknt
t
n

Guess the 0-order solution:

an( 0 ) t

Use this guess to solve the equation and to get the 1st-order approximation:

dak(1) t
i
k H p n an( 0 ) t e iknt
dt
n

ak(1) t

Use the 1st-order to get the 2nd-order approximation and so on.

dak( p ) t
i
k H p n an( p 1) t e iknt
dt
n
6

First order approximation

dak(1) t
i
k H p n an( 0 ) t eiknt
dt
n
Guess the 0-order solution:

an( 0 ) t ni

Suppose the simplified perturbation:

H kn'
k Hp n
0

Constant between 0 and

Otherwise

k Hp n
H kn'
0

t
0

First order approximation

i kn t
'
H

e
nm ni

da t
i

dt

(1)
k

i a

(1)
k

It was used:

'
ik

i ki t

Otherwise

' i kn / 2
ik

dt 2 H e

e dx 2e
ikx

Between 0 and

ikx / 2

sin ki / 2
ki

sin kx / 2
k

Transition probability

Pik ak 4 H
2

0.8
2

sin 2 ki / 2
2 ki2
In this derivation for constant
perturbation, only transitions
with ~ 0 take place.

1.0

If the perturbation oscillates

harmonically (like a photon),
0 can occur.

0.6

sin( ) /

' 2
ik

0.4

The final result for the Fermis

Golden Rule is still the same.

0.2
0.0

Physically meaningful quantity

1
Wk Pik '
k ' near k
k , k
i
Near k: density

of states

dn
k
dE

1
1

Wk Pik ' Pik k dEk Pik k dki

k ' near k

10

Physically meaningful quantity

Wk

Using

1
1

dE

Pik k dki

ik '
ik k
k

k ' near k

Pik 4 H

' 2
ik

sin 2 ki / 2
2 ki2

1
1 sin 2 ki / 2
' 2
Wk 4 H ik k
dki
2

ki

/2
2 ' 2
Wk
H ik k

11

Fermis Golden Rule: photons and molecules

H H0 d E

Transition rate:

H0 Non-perturbated molecular Hamiltonian

d E Light-matter perturbation Hamiltonian
Wk

2
i d k e iik t Edt k

0
k , k

i
12

Transition dipole moment

Wk

2
i d k e iik t Edt k

i d k i e

N at

Z R r
n 1

N el

m 1

k d N ik i d e k

k , k

Electronic
transition
dipole moment

i
13

Einstein coefficients

(see Einstein coefficients text in the course hom

Wika Bik N i

Rate of absorption i k

Einstein coefficient B for absorption

1 gk
Bik
i de k
2
6 0 g i

g n - degeneracy of state n
k

ik
ik
Ni

14

Einstein coefficients
Rate of stimulated emission k i

Wkist Bki N k

Einstein coefficient B for stimulated emission

gi
Bik
Bki
gk
Nk

ki
ki

15

Einstein coefficients
Rate spontaneous decay k i

Wkisp Aki N 2

Einstein coefficient A for spontaneous emission

ki3
Aki 2 3 Bki
c
Nk

k
ki
ki
i

16

Einstein coefficient and oscillator strength

2 0 mc 3
f ki
Aki
2 2
ki e
In atomic units:

c3
f ki
Aki
2
2Eki

17

Einstein coefficient and lifetime

3

1
c
ki

Aki
2E 2 f ki

1
If E21 = 4.65 eV and f21 = -0.015,
what is the lifetime of the excited state?

E21 4.65 eV
4.65 / 27.211396
0.170884 au
3

(137)
21
2(0.170884) 2 (0.015)
0.29 1010 au

Converting to nanoseconds:

21 0.29 1010 2.4189 10 17 s

70 ns
18

non-adiabatic transition probabilities

19

Non-adiabatic transitions
Problem: if the molecule prepared in state 2 at x = moves through a region
of crossing, what is the probability of ending in state 1 at x = ?
E

2 , 2

1 , 2
H22
0

E2
H12

H11
E1

1 , 1

2 , 1

0
20

Models for non-adiabatic transitions

1. Landau-Zener

H11 H 22 F12 x
H12 , F12 constant

2
2 H12
P exp

v F12

2. Demkov / Rosen-Zener

E1 E2 constant

h12 h12x sech x /

3. Nikitin

H11 H 22 A cos 0 exp x

A
H12 sin 0 exp x
2
4. Bradauk; 5. Delos-Thorson; 6.

E1 E2
P sech
x

vh

12
2

exp cos 2 0 / 2 1
P
exp 1
2

tan 2 0 cot 2 0
v
21

Derivation of Landau-Zener formula

i t

an t exp H nn t dt n

H 0
t

Multiply by

at left and integrate

dak t
i
H kn an t e n
dt
n k

H kn k H n
i t
n H nn dt

In the deduction it was used:

d t
H nn dt H nn

dt
22

Since there are only two states:

dak t
H kn an t e n
dt
nk

da1 t
i
H12 a2 t e 21
dt

(i)

da2 t
i
H 21a1 t e 12
dt

(ii)

ij i j
Solving (i) for a2 and taking the derivative:

H11 H 22 e da1 ie d 2 a1 t da2 t

(iii)
2
12

H12

12

dt

H12

dt

dt

Substituting (iii) in (ii):

d 2 a1 i
da1 1
2
H11 H 22
2 H12 a1 0
2
dt

dt
23

d 2 a1 i
da1 1
2

H
11
22
12 a1 0
2
2
dt

dt
Zener approximation:

H11 H 22 t
H11 F1 x F1vt

2 , 2

dH 22
F2
dx

1 , 1

H 22 F2 x F2 vt
dH11
F1
dx

1 , 2
2 , 1

H11 H 22 F1 F2 vt

F12 v

0
24

d 2 a1 i
da1 1
2

F
vt

H
12
12 a1 0
2
2
dt

dt
d 2 a2 i
da2 1
2

F
vt

H
12
12 a2 0
2
2
dt

dt
Problem: Find a2(+) subject to the initial condition a2()
The solution is:

= 1.

2
H12
a2 exp

v F12

a2 1

a1 ?

a1 0

a2 ?

(The complete derivation

is in the paper on LandauZener in the course
homepage)

x
0

25

The probability of finding the system in state 2 is:

Pnad a2

2
2 H12
exp

v F12

The probability of finding the system in state 1 is:

Pad 1 Pnad
1

2
2 H12
1 exp

v F12

Probability

Pad
Pnad

Pnad

Pad

0
0

|H12|

| F12| or v

26

Example: In trajectory in the graph, what are the probability of the molecule to remain
in the * state or to change to the closed shell state?

P * *

F12 v

H12
exp 2

H11 H 22 t

0.03224 0.01126
0.0435 au/fs 0.001 au

1 au

time

2.4 10 2 fs

H22 = t

Energy (au)

-224.65

cs

H12 = au

-224.70

-224.75
-224.80

cs

H11 = t

-224.85
0

Time (fs)

10

12

14

27

Example: In trajectory in the graph, what are the probability of the molecule to remain
in the * state or to change to the closed shell state?

P * *

0.011577 2
exp 2
0.43
0.001

P *cs 1 P * * 0.57
0.57

Energy (au)

-224.65

cs

-224.70

-224.75

0.43

-224.80

cs
-224.85
0

Time (fs)

10

12

14

28

For the same H12, Landau-Zener predicts:

Adiabatic

Non-adiabatic (diabatic)
E

v
H12

x
0

Pnad

2 H12
exp

v F12
2

29

For the same h12 , Rosen-Zener predicts:

Adiabatic

Non-adiabatic (but not diabatic!)

E

v
v
0

x
0

Pnad

E1 E2
sech
x

vh

12

x
0

30

For the same 0 (H12), Nikitin predicts:

Adiabatic

Non-adiabatic (diabatic)
E

exp cos 2 0 / 2 1
Pnad
exp 1
2

tan 2 0 cot 2 0
v

x
0

31

The problem with the previous formulations is that

they only predict the total probability at the end of
the process.
If we want to perform dynamics, it is necessary to
have the instantaneous probability.

32

Next lecture
Quantum dynamics methods

Contact
mario.barbatti@univie.ac.at
This lecture can be downloaded at
http://homepage.univie.ac.at/mario.barbatti/femtochem.ht
ml
lecture6.ppt

33