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module14_01

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08/23/2014

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MODULE 14Time-dependent Perturbation Theory
In order to understand the properties of molecules it is necessary to see how systems respond tonewly imposed perturbations on their way to settling into different stationary states. This is particularly true for molecules that are exposed to electromagnetic radiation where the perturbation is a rapidly oscillating electromagnetic field. Time dependent perturbation theoryallows us to calculate transition probabilities and rates, very important properties in thePhotosciences. The approach we shall use is that for the time-independent situation, viz., examine a two-statesystem in detail and then outline the general case of arbitrary complexity.
The two-state system
We can write the total hamiltonian for the system as the sum of a stationary state term and atime-dependent perturbation
!"#"
\$\$\$"
HHH
= +
and suppose that the perturbation is one that oscillates at an angular fre%uency,
ω
, then
#"#"
\$\$"&cos
HtH
ω
=
where
#"
\$
H
is the hamiltonian for a time-independent perturbation and the factor & is for later convenience. 'ur time-dependent (chr)dinger e%uation is \$
Hi
δ δ
ΨΨ =
h
*s before we consider a pair of eigenstates #and & representing the time-independent"wavefunctions
#
ψ
and
&
ψ
with energy eigenvalues
E
1
and
E
2
. These wavefunctions are thesolutions of the e%uation
!"
\$
n n n
H
ψ ψ
=
and are related to the time-dependent functions according to
+
"
n
iE n n
t e
ψ

Ψ =
h
#

When the perturbation is acting the state of the system can be expressed as a linear combinationof the basis functions defined by the set in e%uation #.". We confine ourselves to ust two of them and the linear combination becomes
##&&
"""""
tattat
Ψ = Ψ + Ψ
/otice that we are allowing that the coefficients are time-dependent because the composition of the state may evolve with time. The overall time dependence of the wavefunction is partly dueto the changes in the basis functions and partly due to the way the coefficients change with time.*t any time
t,
the probability that the system is in state
n
is given by
&
"
n
a
. (ubstitution of e%uation #.0" into the (chr)dinger e%uation #.1" leads to the following
!"#"!"#"####&&&&##&&##&&##&&
\$\$\$\$\$"""
HaHaHtaHaHiaaaaiaiiaittt
δ δ δ δ δ δ δ δ δ δ
Ψ = Ψ + Ψ + Ψ + Ψ= Ψ + ΨΨ Ψ= + Ψ + + Ψ
hh h h h
/ow each of the basis functions satisfies the time dependent (chr)dinger e%uation, viz.
!"
\$
nn
Hi
δ δ
ΨΨ =
h
so the last e%uation in #.2" simplifies down as
#"#"##&&##&&
\$\$""
aHtaHtiaia
Ψ + Ψ = Ψ + Ψ
& &h h
where the dots over the coefficients signify their time derivatives. /ow we expand the laste%uation by explicitly writing the time dependence of the wavefunctions
#&#&
++#"#"#&++#&
\$\$"#"&#&
iE t iE iE t iE
a H t e a H t ei a e i a e
+= +
h hh h
& &h h
/ow multiplying from the left by the bra #and use the orthonormality relationship we find
#&#
+++#"#"###&#&#
""
iE t iE t iE
a H t e a H t e i a e
+ =
h h h
&h
where the matrix elements are defined in the usual way. /ow we write
&#&#
E
ω
=
h
when wefind that #.##" becomes
&#
#"#"###&#&#
""
i
a H t a H t e i a
ω
+ =
&h
&

It is not unusual to find that the perturbation has no diagonal elements so we put
#"#"##&&
""!
HtH
= =
*nd then e%uation #.#&" reduces to
&#
#"&#&#
"
i
a H t e i a
ω
=
&h
or, rearranging
&#
#"#&#&
#"
i
a a H t ei
ω
=
&h
this provides us with a first order differential e%uation for one of the coefficients but it containsthe other one. We proceed exactly as above to obtain an e%uation for the other coefficient
&#
#"&#&#
#"
i
a a H t ei
ω
=
&h
In the absence of any perturbation, the two matrix elements are both e%ual to zero and the timederivatives of the two coefficients also become zero. In which case the coefficients retain theiinitial values and even though
Ψ
oscillates with time, the system remains frozen in its initially prepared state.  /ow suppose that a constant perturbation, 3, is applied at some starting time and continued untila time later. To allow this let us write
#"#"#&&#
"and"4
H t V H t
= =
h h
where we have invo5ed the 6ermiticity of the hamiltonian. Then
&#&#
#&&#
4
i t i
a iVa e a iV a e
ω ω
= =
& &
This is a pair of coupled differential e%uations, which can be solved by one of several methods.'ne solution is
&#
+&&
""
i i t i
a t Ae Be e
ω
= +
where
A
and
B
are constants that are determined by the initial conditions and
is given by
&&#+&&#
#,"&
ω
Ω = +
* similar expression holds for

a
1
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