Section 5.

Time dependent perturbations

Show how time dependence in quantum

mechanics leads to transitions between energy
levels

Absorption and emission of radiation by atoms

5.1 Time-dependent perturbation theory

We aim to solve the time-dependent

Schrodinger equation
∂ψ
Ĥψ = iℏ
∂t
where
Hˆ (r , t ) = Hˆ 0 (r ) + Hˆ ′(r , t )

As in section 4, Ĥ 0 is the Hamiltonian of the

unperturbed system, and does not depend on
time. We assume we know its eigenvalues and
eigenfunctions, ie solutions of
Hˆ 0 φn = En φn

The difference now is that the perturbation Ĥ ′

depends on time
We expand the wavefunction ψ (r , t ) in terms of
the eigenfunctions of Ĥ 0
ψ (r , t ) = ∑ cn (t )φn (r )exp(−iEnt / ℏ)
n

Note that the coefficients cn depend on time

Ĥψ becomes

∑ c (t ) ( E
n
n n + Hˆ ′) φn (r )exp(−iEnt / ℏ)

∂ψ
iℏ becomes
∂t
 i cn En dcn 
iℏ ∑  − + φn ( r )exp(−iEnt / ℏ)
n  ℏ dt 
Equating these and simplifying gives
dcn
iℏ ∑ φn (r )exp(−iEnt / ℏ) =
n dt
∑ cn (t ) Hˆ ′φn (r )exp(−iEnt / ℏ)
n

Multiply both sides by φm∗ (r ) , integrate, and use

orthogonality:

dcm 1
= ∑ cn (t ) H m′ n (t ) exp ( i ωmn t )
dt iℏ n
where
H m′ n (t ) = ∫∫∫ φm∗ (r ) Hˆ ′(r , t ) φn (r ) d 3r

and
Em − En
ωmn =
ℏ
We want to solve (2) for the coefficients cm (t ) .
We assume that the perturbation is switched on
at time t = 0 , and that the system is in the
eigenfunction φi (r ) at that time, ie
ci (t = 0) = 1, c m (t = 0) = 0 for all m ≠ i

If the perturbation Ĥ ′ is weak, we can assume

that all the cm for m ≠ i are small, and that ci
remains at 1. (2) then becomes
dcm 1
′ (t ) exp ( i ωmi t )
= H mi
dt i ℏ

which has the solution

t
1
′ (t ') exp ( i ωmi t ') dt '
cm (t ) = ∫ H mi
iℏ 0
What will a measurement of the energy of the
system give?

At t = 0 , the wavefunction of the system is the

eigenfunction φi (r ) and so the energy is Ei

Equations (1) and (6) show how the

wavefunction evolves in time

At any time t the probability of measuring the

2
energy as Em is cm (t )

We can see that the time-dependent

perturbation causes transitions between the
quantum states
5.2 Periodic perturbations

Consider a sinusoidal perturbation of angular

frequency ω :
Hˆ ′(r , t ) = Hˆ ′(r ) cos ωt
1 ˆ
= H ′(r ) [ exp(iωt ) + exp(−iωt ) ]
2

Equation (6) becomes

H ′f i  t
c f (t ) =  ∫ exp ( i ( −ω + ω f i ) t ') dt '
2iℏ  0
t

+ ∫ exp ( i (ω + ω f i ) t ') dt '
0 
with
H ′f i = ∫∫∫ φ ∗f (r ) Hˆ ′(r ) φi (r ) d 3r

E f − Ei
and ω fi =
ℏ
Doing the integrals gives

H ′f i  exp ( i (−ω + ω f i ) t ) − 1
c f (t ) = − 
2ℏ  −ω + ω f i

exp ( i (ω + ω f i ) t ) − 1 
+ 
ω + ω fi 

The first term is peaked for ω = ω f i and the

second is peaked for ω = −ω f i . Only one term is
therefore likely to be significant, and we will
consider only the first.

The probability of finding the system in state

2
φ f (r ) is c f (t )

H ′f i  sin (ω f i − ω ) t / 2  
2 2
2
c f (t ) =  
4ℏ  (ω f i − ω ) / 2 
2

 
As t increases, this “sinc squared” function
becomes very strongly peaked for ω = ω f i , ie
when ℏω = E f − Ei .

There is a high probability of causing a

transition from initial state i to final state f
only if the frequency of the perturbation
matches the energy difference between the
states

If the perturbation is caused by an

electromagnetic wave of angular frequency ω ,
this corresponds to excitation of the quantum
system

Everything works similarly if we look at the

ω = −ω f i peak. This would correspond to
stimulated emission of an excited state
In practice, you don’t get a perturbation that is
purely sinusoidal for all time. We can treat this
by saying that the perturbation includes a range
of frequencies, where the “density” of
frequencies between ω and ω + dω is g (ω ) dω

The total probability of excitation from i to f

is then

 sin (ω f i − ω ) t / 2  
2 2
H ′f i ∞
   g (ω ) dω

P (t ) =
4ℏ 2 ∫  (ω f i − ω ) / 2 
0
 

If g (ω ) is slowly varying with respect to the

sinc-squared function, this becomes
2
π H ′f i
P (t ) = 2
g (ω f i ) t
2ℏ
The transition rate (transition probability per
time) is then
2
π H ′f i
W= 2
g (ω f i )
2ℏ

This is called “Fermi’s golden rule”