PG/KA/Chap 1 - 1

Chap 1. Time-dependent Quantum Theory

Hamiltonian : H = H
0
+ V (q, t)
_
H
0
(time-independent) :
H
0

n
(q) = E
n

n
(q)
steady-state :
n
(q)e
iE
n
t/ h
_
Schrodinger Eq (time-dependent) : ih

t
(q, t) = H(q, t) (1)
Expand (q, t) by {
n
} (= complete orthonormal set)
(q, t) =

n
c
n
(t)
n
(q)e
iE
n
t/ h
Enter into (1) and
k
| (and use orthogonality
k
|
n
=
kn
)
d
dt
c
k
(t) =
i
h

n
e
i
kn
t
V
kn
(t)c
n
(t) (2)
_
V
kn
(t) =
_

k
(q)

V (q, t)
n
(q)dq = k|V (t)|n

kn
= (E
k
E
n
)/ h : transition energy (n k)
_
PG/KA/Chap 1 - 2
Illustration : 2-level system
d
dt
_
c
1
(t)
c
2
(t)
_
=
i
h
_
V
11
(t) e
i
12
t
V
12
(t)
e
+i
12
t
V
21
(t) V
22
(t)
__
c
1
(t)
c
2
(t)
_
Simplifying assumptions
V
11
= V
22
= 0 (V = interaction among dierent states)
V
12
(t) = V
21
(t) = v (const.)
12
= 0 (or E
1
= E
2
)
Then
d
dt
c
1
=
i
h
vc
2
,
d
dt
c
2
=
i
h
vc
1
With c
1
(0) = 1 and c
2
(0) = 0,
c
1
+ c
2
= e
ivt/ h
, c
1
c
2
= e
+ivt/ h
c
1
= cos(vt/ h), c
2
= i sin(vt/ h)
Oscillation period v
1
i.e., larger interaction (v) faster resonance
PG/KA/Chap 1 - 3
Perturbative expansion
Back to (2). Matrix form :
d
dt
c(t) =
i
h
W(t) c(t) ([W(t)]
kn
= e
i
kn
t
V
kn
(t))
Integrate (formally) :
c(t) = c(0)
i
h
_
t
0
W() c()d
Sequential expansion :
c(t) = c(0)
i
h
_
t
0
W() c(0)d +
_
i
h
_
2
_
t
0
d
_

0
d

W() W(

) c(0)
+
_
i
h
_
3
_
t
0
d
_

0
d

0
d

W() W(

) W(

) c(0)
+
PG/KA/Chap 1 - 4
First-order perturbation [SR 4.3.1]
c
(1)
(t) = c(0)
i
h
_
t
0
dW() c(0)
Assume : c
n
(0) =
nm
(initiate from |m at t = 0 )
Other state(s) |k (= |m) at time t :
c
(1)
k
(t) =
i
h
_
t
0
d

n
W
kn
()c
n
(0) =
i
h
_
t
0
dW
km
()
Transition probability |m |k
P
(1)
k
(t) = |c
(1)
k
(t)|
2
=
1
h
2

_
t
0
dV
km
()e
i
km

2
Example 1 : [SR 4.3.2] Excitation of diatomic molecule by collision of atom
PG/KA/Chap 1 - 5
Example 2 : [SR 4.5.1] Time-independent interaction
Assume : V
km
= const. (time independent)
Then
c
(1)
k
(t) = V
km
e
i
km
1
h
km
P
(1)
k
(t) = |V
km
|
2
sin
2
(
km
t/2)
( h
km
/2)
2
P
(1)
k
(t) along E
k
: Peak at E
m
, width 2h/t, height (t/h)
2
width 1/t Short time large energy uncertainty
.
.
.
PG/KA/Chap 1 - 6
Second-order perturbation
c
(2)
(t) = c
(1)
(t) +
_
i
h
_
2
_
t
0
d
_

0
d

W() W(

) c(0)
Assume : c
n
(0) =
nm
(as before)
[W() W(

) c(0)]
k
=

l
W
kn
()W
nl
(

)c
l
(0) =

n
W
kn
()W
nm
(

)
c
(2)
k
(t) = c
(1)
k
(t) +
_
i
h
_
2
_
t
0
d
_

0
d

n
V
kn
()V
nm
(

)e
i
kn

e
i
nm

Transition |m |k via intermediate states |n

_
Examples : Raman scattering
Bridge-mediated electron transfers
_
Important when 1st-order (direct) transitions are forbidden V
km
= 0
PG/KA/Chap 1 - 7
Schrodinger vs Interaction Pictures
Schrodinger picture : ih

t
|
S
(t) = H(t)|
S
(t)
Integrate : |
S
(t) = |
S
(0)
i
h
_
t
0
dH()|
S
()
Sequential expansion : (omit subscript S)
|(t) = |(0)
i
h
_
t
0
dH()|(0)
+
_
i
h
_
2
_
t
0
d
_

0
d

H()H(

)|(0)
+
BUT dealing with the operators H(t) is rather tedious
Interaction picture is often more convenient [H = H
0
+V ]
PG/KA/Chap 1 - 8
Interaction picture
Denition : |
I
(t) e
iH
0
t/ h
|
S
(t)
Eq of motion :

t
|
I
(t) =
i
h
V
I
(t)|
I
(t)
( V
I
(t) e
iH
0
t/ h
V e
iH
0
t/ h
)
_
_

t
|
I
=
i
h
H
0
e
iH
0
t/ h
|
S
+ e
iH
0
t/ h

t
|
S

=
i
h
e
iH
0
t/ h
V |
S
=
i
h
e
iH
0
t/ h
V e
iH
0
t/ h
|
I

_
_
Sequential expansion :
|
I
(t) = |
I
(0)
i
h
_
t
0
dV
I
()|
I
(0)
+
_
i
h
_
2
_
t
0
d
_

0
d

V
I
()V
I
(

)|
I
(0) +
(Compare with the previous page : H(t) V
I
(t) )
PG/KA/Chap 1 - 9
Time-ordered Exponential
Assume : |
I
(0) = |
m
(= |m)
Amplitudes of other states |k (= |m) at time t :
c
k
(t) = k|
I
(t)
= k|1 +
_
i
h
_
_
t
0
dV
I
() +
_
i
h
_
2
_
t
0
d
_
t
0
d

V
I
()V
I
(

) + |m

_
k

exp
+
_
i
h
_
t
0
dV
I
()
_

m
_
(time ordered exponential)
_

_
can be also expressed (formally) via Dyson time-ordering operator P
PA(t
1
)B(t
2
) =
_
A(t
1
)B(t
2
) (t
1
> t
2
)
B(t
2
)A(t
1
) (t
1
< t
2
)
exp
+
_
i
h
_
t
0
dV
I
()
_
= P

n=0
_
i
h
_
t
0
dV
I
()
_
n
= P exp
_
i
h
_
t
0
dV
I
()
_
_

_
PG/KA/Chap 1 - 10
Fermis golden rule
Assume : time-independent V
km
, c
k
(0) =
km
(or |(0) = |m )
P
(1)
k
(t) = |c
(1)
k
(t)|
2
= |V
km
|
2
sin
2
(
km
t/2)
( h
km
/2)
2
(1st-order perturbation) [cf page 5]
Total probability of transition (from |m ) : P
T

k=m
P
(1)
k
(t)
=

k
|V
km
|
2
sin
2
(
km
t/2)
( h
km
/2)
2
=
_
dE(E)|V
m
(E)|
2
sin
2
((E E
m
)t/2 h)
((E E
m
)/2)
2
(E) =

k
(E E
k
) : density of states
As t : P
T

_
dE(E)|V
m
(E)|
2
2t
h
(E E
m
) =
2t
h
(E
m
)|V
m
|
2
Transition rate w
T
=
2
h
|V
m
|
2
(E
m
) Fermis golden-rule
PG/KA/Chap 1 - 11
State-to-state form
t : P
(1)
k
(t) |V
km
|
2
2t
h
(E
k
E
m
)
State-to-state transition rate w
km
=
2
h
|V
km
|
2
(E
k
E
m
)
By summing over the nal states, w
T
is recovered

k
w
km
=
_
dE
k
(E
k
)w
km
=
2
h
|V
m
|(E
m
) = w
T
_

_
Note :
As t :
sin
2
()
()
2
(E
k
E
m
) Energy conservation
Energy width ( = uncertainty) smaller
uncertainty principle ( E t )
_

_
PG/KA/Chap 1 - 12
Periodic interaction : V (t) = Ue
it
(e.g. semiclassical theory of light-matter interaction)
c
(1)
k
(t) =
i
h
_
t
0
dV
km
()e
i
km

=
i
h
_
t
0
dU
km
e
i(
km
)
Use the previous results, replace V
km
U
km
,
km

km

Total transition rate

w
T
=
2
h
|U
km
|
2
(E
m
h)
State-to-state form
w
km
=
2
h
|U
km
|
2
(E
k
E
m
h)