MIT Department of Chemistry

5.74, Spring 2004: Introductory Quantum Mechanics II

p. 1
Instructor: Prof. Andrei Tokmakoff
5.74 TIME-DEPENDENT QUANTUM MECHANICS
The time evolution of the state of a system is described by the time-dependent Schrdinger
equation (TDSE):
r, t ( ) i

( ) = H

r, t
t
Most of what you have previously covered is time-independent quantum mechanics, where we
mean that H

is assumed to be independent of time: H

= H r

( ).
We then assume a solution of the form:
(r, t)= r ( )
1
( ) =
H r ( )
( )T t

( ) r
i T t
( ) t r T t ( )
Here the left-hand side is a function of t only, and the right-hand side is a function of r only.
This can only be satisfied if both sides are equal to the same constant, E
Time-Independent
Schrdinger Eqn.
H r

( )
( )
= E H r ( ) = E r

( ) r

( ) r ( )
r
H is operator corresponding to E
Second eqn.:
1 T
|
iE
|
i = E T t ( ) = 0
T t ( ) t
\
t
+

.
Solution: T t ( )= Aexp(iEt / )= Aexp(it)
p. 2
r So, for a set of eigenvectors ( ) with corresponding eigenvalues E
n
, there are a set of
n
corresponding eigensolutions to the TDSE.
r, t ( )= a (r) exp(i t) = E /
n n n n n n
The probability density

*
P = (r, t)(r, t)d
may be time dependent for ( r , t ) , but is independent of time for the eigenfunctions ( r , t ) .
r, t ( ) r = r, t ( )
n
Therefore, r ( ) are called stationary states.
However, more generally a system may be represented as a linear combination of eigenstates:
i t
(r, t)=

c (r, t) =

c e
n
(r)
n n n n
n n
For such a case, the probability density will oscillate with time: coherence.
e.g., two eigenstates
i
1
t
+ c
2

2
e
i
2
t
(r, t)= c
1

1
e
2 2
*
i
(

1
t
)
+ c
*
+i
(

)
t
*
p t
( )
= = c
1
+ c
2
+ c
1
c
2

2
e c
1

1
e
1 2 1 2 2
probability density oscillates as cos(
2
)t
1
This is a simple example of coherence (coherent superposition state). Including momentum (a
wavevector) of particle leads to a wavepacket.
1
p. 3
TIME EVOLUTION OPERATOR
More generally, we want to understand how the wavefunction evolves with time. The TDSE is
linear in time. Since the TDSE is deterministic, we will define an operator that describes the
dynamics of the system:
(t) =U t, t
0
( )(t
0
)
For the time-independent Hamiltonian:
( )+
iH
r , t

r , t ( )= 0 (1)
t
To solve this, we will define an operator T = exp(iHt / ), which is a function of an operator.
A function of an operator is defined through its expansion in a Taylor series:
1
|
iHt
|
2
T = exp
|
iHt
|
= 1
iHt
+
2!
\

.


= f H ( )
1
Multiplying eq. 1 from the left by T

= exp(iHt / )we have:

exp
|
iHt
|
( )
(
(
= 0
\

.
r , t

integrating t
0
t :
( )
exp
|
iHt
0
|
r , t
0
exp
|
iHt
|
r , t
( )
= 0
\

. \

.
( )= exp
|

H t t
0
( )
= U t, t
0
r, t
0
r, t
( )
|
|
r, t
0
( ) ( )
\ .
For functions of an operator A : Given a set of eigenvalues and eigenvectors of A , i.e.,
A = a
n
, you can show by expanding the function as a polynomial that f
( )
( ) A

= f a
n n n n n
p. 4
(r , t) = e
E
n
(t t
0
)/
(r, t
0
)
n n
or, alternatively, if we substitute the projection operator (identity relationship)
iH t t
0
) / (
U t, t ) = e

(
0 n
E
n
n
=
n
i
n
(t t
0
)

=

e
n


n n
n
This form is useful when are characterized; well develop U t, t
0
( ) more later. So now we
n
can write our time-developing wave-function as
i
n
(t t
0
)
( r , t ) =

e ( r , t
0
)
n n n n
n
i
n
(t t
0
)
c
n
( ) =

e t
0 n
n
Time-evolution of a coupled two-level system (2LS)
It is common to reduce or map problem onto a 2LS. We then discard remaining degrees of
freedom, or incorporate them as a heat bath, H H
0
+ H
bath
. =
Lets discuss the time-evolution of a 2LS with a time-independent Hamiltonian.
Consider a 2LS with two (unperturbed) eigenstates and
b
with eigenenergies and
b
,
a a
which are then coupled through an interaction V
ab
.
V

a
H = a a + b
b
b + a V
ab
b + b V
ba
a
a
2
|

a
V
ab
|
=

\V
ba

b
.
|

-
*
Since the Hamiltonian is Hermetian, (H
ij
= H
ji
), we suggest
p. 5
* i
V
ab
= V
ba
= Ve

Ve
i
| |
a
i
H =
\

Ve
+

b .
|
If we define the variables
+
b a
E =
2

b a
=
2
Then we can solve for the eigenvalues of the coupled systems:

= E
2
+ V
2
Because the expressions get messy, we dont choose to find the eigenvectors for the coupled
system,

, using this expression. Rather, we use a substitution where we define:
V
tan 2 =
2


(0 < < /2)
i
| |1 tan 2 e
=
i
H E I +

\
tan 2 e
+
1
.
|
We now find that we can express the eigenvalues as

= E sec2
We now want to find the eigenstates of the Hamiltonian, H

, =

where e.g. = c + c
b
:
+ a a

b
i / 2 i / 2
cos e

sin e

=
=
+
+
a

b
i / 2 i / 2
sin e

cos e


+
a

b
=1 Orthonormal complete + orthogonal:
a
+
a b

b
V
p. 6
Examine the limits:
(a) Weak coupling (V/ << 1). Here 0, and
+
corresponds to perturbed by the V
ab a
interaction. corresponds to .
(
For 0 ;
)

+ a

b
(b) Strong coupling (V/ >> 1). Now = 45, and the a/b basis states are indistinguishable.
The eigenstates are symmetric and antisymmetric combinations:
~
1
( )

b a
2
Whether + or corresponds to the symmetric or asymmetric combination depends on whether V
is positive or negative. (For V >> , = 45)
We can schematically represent the energies of these states:

+
-

b
a


These eigenstates exhibit avoided crossing.
p. 7
The time-evolution of this system is given by our time-evolution operator.
e

+
(t t
0
)

+
e
i

(tt
0
)
U t, t
0
+ ( ) =
+

Now and
b
are not the eigenstatespreparing will lead to time-evolution!
a a
. Lets prepare the system so that it is initially in state
a
(t
0
= 0) (0) =
a
What is the probability that it is found in state
b
at time t ?
2
2
t P
ba
( ) =
b
t ( ) = U t, t
0
( )
b a
To evaluate this, you need to know the transformation from the
a,b
to the

basis, given
above. This gives:
t P
ba
( ) =
V
2
V
2
2
sin
2

R
t
+
where the Rabi Frequency
R
=
1

2
+ V
2

R
represents the frequency at which probability amplitude oscillates between and
b
states.
a
V
2
2
ba
( )
V
2
+
P t
0 t = R
t
/
Notice for V 0

a,b
(the stationary states), and there is no time-dependence.
V
For V >> , then
R
= and P =1 after t = = .
2
R
2V
p. 8
TIME-INDEPENDENT HAMILTONIAN
There are two types of values that we often calculate:
Correlation amplitude: C t ( ) = t ( )
measures the resemblance between the state of your system at time t and a target state
( . The probability amplitude P t) = C t ( )
2
for a set of eigenstates
n
C t = t = U t, t
0
) ( ) ( ) ( (0)

j
t
c m
*
=

j e j n c
m n
m,n , j
*
n
i t
=

c c e
m n
n
Expectation values: A t ( ) = t ( )A(t)

n
t
( ) = t

e c =

c
n n n n
n n

m
t *
t ( ) =

e c
m

m
m
E E
n m
*
i t

=
nm nm
A t ( ) =

c c e A
m n m n
m,n

n m
*
t t =

c ( )c ( )A
m n mn
m,n
p. 9
DENSITY MATRIX
For a system described by a wavefunction =

c ( t ) n we showed (t )
n
n
A t ( ) = (t)A(t)
*
t =

c
( )
c
( )
m An t
m n
n, m
We will often find it useful to define a density operator
t
( )

(
t
)

(
t
)
*
t t =

c ( )c ( ) n m
n m
n,m
m (by definition) =

nm
( )
n t
n,m
are the density matrix elements. Substituting, we see that
nm
A t ( ) =

A (t)
mn nm
n,m
= Tr A t
|
( )
|
( ( (
2) invariant to unitary transformation Tr S AS
)
= Tr A
Trace Properties: 1) cyclic invariance Tr ABC )= Tr CAB) = Tr BCA )
(

( )
Pure vs. Mixed States
Why would we need the density matrix? It helps for mixed states.
1) pure states: a system characterized by a wavefunction (previous page)
2) mixed states: not characterized by single wavefunction
> statistical mixturesensemble at thermal equilibrium
> independently prepared states
> no phase relationship between elements of mixture
p. 10
For an ensemble of systems with a probability p
k
of occupying quantum state
k
, with

p
k
= 1
k
( ) =

p
k

k
( t ) A t A
k
( t )
k
t t ( )

p
k
( )
k
( ) t
k
k
( ) = Tr A( )( A t

t

Properties:

*
1) is Hermetian =
nm mn
2) Tr()=1 Normalization
Tr
2
( )
=1 for pure state
3)
< 1 for mixed state
Lets look at the density matrix elements for a mixture:
= n m =

p n m
nm k

k
k
k
where

c n =
k n
n
k
c : expansion coefficient for
n
eigenstate n of wavefunction k
k k
c =

p c
n
( )
*
k m
k
*
= c c coefficients for eigenstate averaged over mixture
n m
Diagonal elements (n = m)
2
k *
=

p c =c c = p
nn k n n n n
k
probability of finding a system in mixture in state n
POPULATION ( 0)
p. 11
Off-Diagonal Elements (n m) complexhave phase factor
describe the evolution of coherent superpositions.
COHERENCES
For an arbitrary state , the expectation value of the density matrix:

gives the total probability of finding a particle in the pure state within the mixture.
We will sometimes refer to the density matrix at thermal equilibrium
0
( or
eq
), which is
characterized by thermally distributed populations in the quantum states
E
n
= p =
e
nn n
Z
where Z is the partition function. More generally, the density matrix can be defined as
H
=
e
Z
where Z = Tr(e
H
). For H n =E n ,
n
n | e
H
= | m
nm
E
n
= e
nn
p. 12
TIME-EVOLUTION OF DENSITY MATRIX
Follows naturally from definition of and T.D.S.E.

=
i i

H = H
(
H = H
)
t t


(
= ( = +
(
t t

t t

i i
= H + H


i
= |H, |
t
Liouville-Von Neumann Eqn.
For a time-independent Hamiltonian:

nm
( ) = t n (t m = n ( t ) ( t m ) )
(

n
(t t
0
)
t = U t, t
0
) ( t
0
) =

n e n ( t
0
) ( )
ni
t

n
(t t
0
) i +
m
(t t
0
) i
( ) = e n ( ) ( )
nm
t
0
t
0
m e
i
= e

nm
(t t
0
)

nm
( ) t
0
E E
n m
=
nm

Populations: ( ) =
nm
( t
0
) time-invariant t
nn
Coherences: oscillate at energy splitting
nm