Chapter Four

Time- Dependent Quantum Mechanics

Formal Theory

1. State of Quantum System is described by a wave function ψ or a

\ α 〉.
2. Dynamical variables are represented by operators Ω .
3. There are three ways to formulating time dependant Quantum
mechanics;

i) Schrödinger Picture: time dependent state function \ α ( t )〉 .

ii) Heisenberg Picture: time dependent operators Ω ( t ).
iii) Interaction Picture: time dependent in both \ α ( t )〉 and Ω ( t ).

I.) Schrödinger Picture:

S.E. can be rewrite as;

d
ih | α s (t )〉 = H | α s (t )〉 .........( 1 )
dt
The total time derivative is used here since the dependent of ket on
coordinate or other variable does not appear explicitly.
Since H is a hermitical, one can write;
d
− ih 〈α s (t ) |= 〈α s (t ) | H .........( 2 )
dt
When H is time- independent, the solutions of the last two equations can
be easily obtain to be;

| α s (t )〉 = e −iHt / h | α s (0)〉

And;
〈α s (t ) |= 〈α s (0) | e iHt / h ............( 3 )
The time rate of change of the matrix element of a dynamical variables
Ω s in the Schrödinger picture is;

d d  ∂Ω s
〈α s (t ) | Ω s | β s (t )〉 =  〈α s (t ) |Ω s | β s (t )〉 + 〈α s (t ) | | β s (t )〉 +
dt  dt  ∂t
d 
〈α s (t ) | Ω s  | β s (t )〉 
 dt 

∂Ω s i i
= 〈α s (t ) | | β s (t )〉 + 〈α s (t ) | HΩ s | β s (t )〉 − 〈α s (t ) | Ω s H | β s (t )〉
∂t h h

∂Ω s 1
= 〈α s (t ) | | β s (t )〉 + 〈α s (t ) | Ω s H − HΩ s | β s 〉 .......( 4 )
∂t ih

The first term on the right side is that part of the change in the matrix
element that arises from any explicit dependence that Ω s may have on the
time, and the second term is that caused by the change in time of the state
function.

It can be easily seen that the dynamical variable is a constant of motion

and all the matrix elements of Ω s are constant in time when;
i) Ω s is commutes with H.
ii) Ω s has no explicit dependence on the time.
II) Heisenberg Picture:

Substituting of equation (3) in to (4) one have;

d
〈α s (0) | e iHt / h Ω s e −iHt / h | β s (0)
dt
∂Ω s −iHt / h
〈α s (0) | e iHt / h
∂t
e
1
ih
{ }
| β s (0)〉 + 〈α s (0) | e iHt / h Ω s e −iHt / h , H | β s (0)〉

[ ]
Where the fact that H , e miHt / h = 0 has been used.i.e.

]ψ = − 2hm ∇   h 2 2 
2
[H , e m iHt / h 2
+ V (r )e m iHt / hψ − e m iHt / h −
  2m
∇ + V (r )ψ = zero


Where, ψ is any time independent state.

Now, define;

| α H 〉 =| α s (0)〉 = e iHt / h | α s (t )〉 .............( 5 )

And;

Ω H (t ) = e iHt / h Ω s e −iHt / h ..........( 6 )

One get;

d ∂Ω H 1
〈α H | Ω H | β H 〉 = 〈α H | | β H 〉 + 〈α H | {Ω H , H } | β H 〉
dt ∂t ih

H.w: show that;

∂Ω H ∂Ω s −iHt / h
i) = e iHt / h e
∂t ∂t
ii) Unless Ω s commutes with H, Ω H depends on t even if Ω s has no
explicit time dependence.
iii) At what time the state function | α H 〉 and | α s 〉 become equal.
Since | α H 〉 does not depend on the time we have;
d dΩ H
〈α H | Ω H | β H 〉 = 〈α H | | βH 〉
dt dt
dΩ H ∂Ω H 1
〈α H | | β H 〉 = 〈α H | | β H 〉 + 〈α H | {Ω H , H }| β H 〉
dt ∂t ih

Since the last equation is valid for an arbitrary bra and ket, we have;

dΩ H ∂Ω H 1
= + [Ω H , H ] ............( 7 )
dt ∂t ih

Notes:

1. The last equation is much similar to the classical equation of motion;

dF ∂F
= + {F , H }
dt ∂t
Where {F, H} is the Poisson braket of the observable F and the energy H.
2. It can be see that, H is the same in both Schrödinger and Heisenberg
pictures.
3. In the Schrödinger picture, the dynamical variables are time invariant,
regardless the explicit time dependence, and the state function vary in
accordance with equation (1).
4. In the Heisenberg picture the state functions are constant in time and
the dynamical variables vary in accordance with equation (7).
5. The transformation from one picture to the other is made with help of
the operator e m iHt / h .
III.) Interaction Picture:

It is fairly obvious that neither the state function alone nor the
dynamical variables alone are central for the description of the
development of a physical system in time.

An especially useful third picture can be specified by dividing the

Hamiltonian into two parts;

H = Ho + H ′ ............( 8 )

Such that Ho does not depend explicitly on the time and also has a
simple structure. For example, Ho might be the kinetic energy and H ′ the
potential energy. Anyway, Ho might be the Hamiltonian for a relatively
simple potential such as the coulomb field and H ′ some additional
interaction such as an external electromagnetic field. Thereby it is
convenient to permit H ′ to depend explicitly on the time.

Now define;

| α I (t )〉 = e iH ost / h | α s (t )〉 ..........( 9 )

Ω I (t ) = e iH ost / h Ω s e −iH ost / h ............( 10 )

So that the interaction and Heisenberg picture are the same when H ′ = 0.
Differentiating equation (9) gives;

d i d
| α I (t )〉 = H os e iH os t / h | α s (t )〉 + e iH ost / h | α s (t )〉
dt h dt

d d
ih | α I (t )〉 = − H os e iH os t / h | α s (t )〉 + ihe iH ost / h | α s (t )〉
dt dt

= − H os | α I (t )〉 + e iH ost / h .H s | α s (t )〉
 = − H os | α I (t )〉 + e iH os t / h H s e −iH os t / h | α I (t )〉

= −e iH ost / h H os e −iH ost / h | α I (t )〉 + e iH ost / h H s e −iH ost / h | α I (t )〉

= e iH ost / h H s′ e − iH os t / h | α I (t )〉

= H I′ | α I (t )〉

Similarly, differentiating of equation (10) gives;

dΩ I ∂Ω I 1
H.w: = + [Ω I , H oI ]
dt ∂t ih

NOTES:

1) It can be seen from equation (8) that the interaction and Heisenberg
pictures are the same when H ′ = 0.
2) In the interaction picture the state functions changes in accordance
with H ′. while the dynamical variables in accordance with Ho.
Time dependent perturbation theory:

It is well know that, one of the most important tasks in Q.M. is the
calculation of the system transition probability from the state n to state m.
in fact, this transition occurs under the influence of the time varying
perturbation H ′( r ,t ) .i.e.

H ( r ,t ) = H o ( r ) + H ′( r ,t ) ...........( 11 )

For example, one may say that, Ho is the atomic or molecular system and
H ′( r ,t ) is the external electromagnetic field. Therefore, equation (11)
may describe an interaction between electromagnetic waves, such as
RFW, MW, IRR, VL, ….etc and matter (Gasses, Liquid and solids).

Basic Theory:

In Q.M. one usually looking for a solution of the equation;

∂ψ
Hψ = ih ............( 12 )
∂t
Now, when H ( r ,t ) takes the form shown in equation (11) and, however,
the unperturbed system is described by;

H oψ n = E onψ n ............( 13 )

Where;

ψ n (r , t ) = ϕ n (r ) exp(−iEont / h ) ............( 14 )

And

∫ ϕ nϕ m dτ = δ nm
*

One may assume that;

ψ (r , t ) = ∑ an (t )ψ n (r , t ) ..........( 15 )
n

It is seen that, this is the same assumption that used previously for
the case of TIP theory except an in equation (15) are time dependent.
Actually, the reason behind made an vary with the time, is that the
perturbation causes a transition from a state to another and the probability
2
of the system to be in a state ψ n at time t is proportional with an ( t ) .

In another word one may say that, before the perturbation is take
place the system is a set or group of atoms or molecules, where there are
no electric or magnetic fields were applied on it. Such a case the system
is describe by equation (13). Whenever, the field is applying on the
system the perturbation will take place. This perturbation is a
consequence of the transition between the different states. However,
where time is going through one may determine the system probability at
any time in which state.

Now, by substituting of equation (15) into (12) one get;

L.H .S = Hψ (r , t )

= {H o + H ′}∑ an (t )ψ n (r , t )
n

= ∑ a n (t ) E onψ n ( r , t ) + ∑ a n (t ) H ′ψ n ( r , t )
n n

∂  
R.H .S = ih ∑ an (t )ϕ n (r ) exp(−iE on t / h )
∂t  n 

= ih∑ a& n (t )ψ n (r , t ) + ∑ Eon a n (t )ψ n (r , t )

n n

Equating the two sides;

∑ {a n H ′ − iha& n }ψ n = 0
n

Multiplying this equation from the left by ψ k* and executing the

integration over all of the space one get;

 it 
∑ {an ∫ ϕ k* H ′ϕ n dτ − iha& n ∫ ϕ k*ϕ n dτ }. exp h ( Eok − E on ) = 0
n

Assume that;

( H ′) kn = ∫ ϕ k* H ′ϕ n dτ

And

E ok − E on
ω kn = ≡ Angular Boher frequency
h

The last equation becomes;

∑ {a n ( H ′) kn − iha& nδ kn }exp(iω kn t ) = 0
n

Or;

i
a& k (t ) = − ∑ an (t )( H ′) kn exp(iω knt )
h n
................( 16 )

Equation (16) represent the time variant for ak. In order to determine the
value of ak, one have to executing the integration and hence the form of
ψ ( r ,t ) will be known in accordance with equation (15).

i
H.W: Show that; a k( s ) (t ) = − ∑
h n
a n( s−1) (t )( H ′) kn e iωknt

Hint: expand an in terms of the perturbation factor λ as before and

making use the relation H o + λH ′.
Starting condition:

In order to deduce ak(t) from equation (16), one needs to now an

initial conditions revel the values of an(t) before and after the
perturbation. Let the perturbation starts at time t, where the system in
state j, i.e. aj(t)=1. Thus an(t)=0 for any state n such that n ≠ j .

Remark: it should be mention that the value of the coefficient aj will

decreases with time, while an increases in the sense that;
∑ ck
2
= 1 remain valid.
k

Accordingly, integration of equation (16) yield to;

t
i 2 iω t
h t∫
a k (t 2 ) − a k (t1 ) = − ( H ′) kj e kj dt
1

Or;
t
i 2 iω t
a k (t 2 ) = a k (t1 ) − ∫ ( H ′) kj e kj dt
ht
1

Case I: k ≠ j
Since ak(t1) equal to zero, thus;

t
i 2 iω t
a k (t 2 ) = − ∫ ( H ′) kj e kj dt ............( 17 )
ht
1

Case II: k=j

t
i 2 iω t
a k (t 2 ) = 1 −
ht∫ ( H ′) kj e kj dt
1

But ω jj = 0

it 2

∴ ak ( t 2 ) = 1 − ∫ ( H ′ )jj dt .............( 18 )
ht 1
Applications:

1) Step- Function Perturbation

H ′(t) = [ 0
H′
t 〈0
t ≥0

It is clear that; a j (0) = 1 and an (0) = 0 for any n ≠ j . For the first
approximation;

I. Case i: k=j

From equation (18);

t
i
a j ( t ) = 1 − ( H ′ )jj ∫ dt
h 0

i
∴ a j ( t ) = 1 − ( H ′ )jj t
h

H.W: What happen to the probability of the system to be in state j with

increasing of (a) time, (b) value of the perturbation field.

II. Case ii: k ≠ j

From equation (17);

t
i
a k (t ) = − ( H ′) kj ∫ exp(iω kj t ) dt
h 0

( H ′) kj
a k (t ) =
hω kj
{1 − exp(iω kj t )}

Where;
t t

∫e
iωkj t
.dt =
1
iω kj
e
iωkjt
=
1
iω kj
{e iωkj t
}
−1
0 0
Now the probability of the system to be in state k (i.e. the probability that
the system was transit from state j at t=0 to state k at t=t) is;
2
Pk (t ) = a k (t )

2
2( H ′) kj  ( E ok − E oj ) 
= sin 2  t ...........( 19 )
Eok − E oj  2h 
Notes:
1. If ( H ′) kj << ( Eok − Eoj ), then ak<<1. (Discuss)
2. The plot of Pk(t) is;

1
sin 2 ( ω kj t ) / ω kj2
2

ωkj
− 6 π − 4π − 2π 0 2π 4π 6π
t t t t t t

This figure shows an important point, that the transition probability

increases as long as the levels become closes.
3. When the levels become much close to each others, the level Eoj can
not be distinguish. For such a case, one have to investigate the transition
from the state j to a dense of state around j and not individual transition
from j to k. However, the total probability is;

+∞
Pt (t ) = ∑ Pk (t ) = ∫ Pk (t ).ρ ( Eok )dEok ............( 20 )
k −∞

ρ( Eok )

Eoj
Where ρ ( Eok ) is the final density of states per unit Eok around Eok. Now,
from equation (19) and (20) one may obtain;

+∞
2 {
sin 2 ( E ok − E oj )t / 2h }
Pt (t ) = ∫ 4 ( H ′) kj
( E ok − E oj ) 2
ρ ( E ok )dEok
−∞

( Eok − Eoj ) 2h
Let x= t ⇒ dEok = dx
2h t
+∞
2 2t sin 2 x
h −∫∞ x 2
∴ Pt (t ) = ( H ′) kj ρ ( Eok ) dx

2 2t
= ( H ′) kj ρ ( Eok ) π
h

Thus, the transition probability rate is;

dPt 2π 2
Tp = = ( H ′) kj ρ ( Eok ) .............( 21 )
dt h

Equation (21) called Fermi's Golden Rule which is an important

equation in the problem of transition and scattering.
2) Harmonic Perturbation:

Let H ′(r , t ) = H ′(r )(2 cos ωt ) 0 ≤ t ≤ to

= zero Otherwise

Note that H ′( r ) is time independent. Now, start from the conditions

a j ( 0 ) = 1 and an ( 0 ) = 0 where n ≠ j , one have from equation (17);

t
i o
a k (t o ) = − ∫ ( H ′) kj exp(ω kj t ) dt ............( 22 )
h0

Where;

( H ′) kj = k | H ′ | j (2 cos ωt )

In order to evaluate the integration in equation (22), it is convenient to

write;

H ′(r , t ) = H ′(r )(e iωt + e − iωt )

Thus;

to

∫ {e }dt
i i (ωkj +ω ) t i (ωkj +ω )t
a k (t o ) = − k | H′| j +e
h 0

 e i (ω kj +ω )t − 1 e i(ωkj −ω )t − 1
= − k | H′| j  +  ...........( 23 )
 h (ω kj + ω ) h (ω kj − ω ) 

Notes:
1. When the angular momentum of the perturbation field ω approaches to
− ω kj (i.e. ω ≈ −ω kj ), the first term in equation (23) become the dominant

in determine the value of ak. This mean that, the incident photon hω will
cause the system to transit from the upper state (Eoj) to the lower state
(Eok). In fact, such a transition called Stimulated Emission.

Eok = Eoj − hω

Graphically, this transition may represented as follows;

Eoj

hω 2 hω

Eok
Simulated Emission

2. For the case when the perturbation field angular momentum ω

approaches to + ωkj (i.e. ω ≈ +ωkj ), the second term in equation (23) will
be the dominant in specifying the value of ak. This happen when;
Eok = Eoj + hω

i.e. the incident photon ( hω ) will leads the system to transit from the
lower state (Eoj) to the upper state (Eok). This transition called Resonant
Absorption and represented graphically as below;

Eok

hω

Eoj
Resonant Absorption
3. If the value of ω is faraway from ωkj , the value of a k will be so small
and hence there is no transition.
4. The system probability to be transit from state j to k is;

 1 
sin 2 (ω kj − ω )t o 
2 2
 2 
Pk (t ) = a k (t ) = 4 k \ H ′ \ j  2 2 
 h (ω kj − ω ) 
 

And the total probability is;

+∞
Pt (t ) = ∫ Pk (t ) ρ f ( E ok )dEok
−∞

The transition rate, however, is given as;

2π 2
T= k |H′| j ρ f ( E ok )
h
 Problems

1.) A linear simple harmonic oscillator consist of a particle of charge (q)

and mass (m). It placed in time dependent homogenous electric field
whose direction is that of the particle displacement;

1 2
E (t ) = ( A / τ )π 2 e −( t / τ )

Where A and τ are constants. If at time t = −∞ the oscillator is in it's

ground state | 0 , show that in the first approximation, the probability that
it well be in it is first excited state | 1 at t = ∞ is;

q 2 A2
P10 = exp( −ω 2 t 2 / 2)
2mhω

2)
a. Drive the selection rule for the transition corresponding to the matrix
element n′l ′m ′ | x | nlm and n′l ′m′ | r | nlm .

b. Identify which of the following are zero;

211 | x | 100 210 | y | 100 200 | y | 100

210 | x | 100 21 − 1 | z | 100 321 | z | 21 − 1

210 | y | 100 210 | z | 100

c. Find the values of the non- zero matrix element from the list in b in
particular show that;

27
211 x 100 = ao
35