15.

5 Schr odingers cat paradox:

A cat is placed in a steel box along with a Geiger counter, a vial of poison, a hammer, and a
radioactive substance. When the radioactive substance decays, the Geiger detects it and triggers
the hammer to release the poison, which subsequently kills the cat. The radioactive decay is a
random process, and there is no way to predict when it will happen. The atom exists in a state
known as a superpositionboth decayed and not decayed at the same time.
Until the box is opened, an observer doesnt know whether the cat is alive or deadbecause
the cats fate is intrinsically tied to whether or not the atom has decayed and the cat would, as
Schr odinger put it, be living and dead ... in equal parts until it is observed.
In other words, until the box was opened, the cats state is completely unknown and therefore,
the cat is considered to be both alive and dead at the same time until it is observed.
The obvious contradiction is that the cat can not be both dead and alive, so there must be a
fundamental aw of the paradox or of the Copenhagen interpretation. Explain what aspect of the
Copenhagen interpretation of quantum mechanics is questioned by this gedanken experiment and
what is wrong with the paradox.
15.6 Time Evolution Operator
15.6.1 Evolution in the basis of eigenstates:
Show that
e

Ht
|
j
= e

E
j
t
|
j
(39)
when |
j
is an eigenstate of

H with eigenvalue E
j
.
15.6.2 Trotter expansion of the time evolution operator:
Show that
e
i

H
= e
iV ( x)/2
e
i p
2
/(2m)
e
iV ( x)/2
+ O(
3
). (40)
Hint: Expand the exponential operators in both sides of Eq. (40) and show that the Trotter expan-
sion is accurate to second order in powers of .
35
15.6.3 Numerical Comparison:
Consider a particle of unit mass (m=1) in a box of unit length (L=1), initially prepared in the
superposition state
(x, 0) =
1

2
(
1
(x)
2
(x))
where
1
(x) and
2
(x) are the eigenstates with eigenvalues E
1
and E
2
obtained by solving the
time-independent Schr odinger equation

H
j
(x) = E
j
)j(x)
Compute the time evolved wavefunction at time t = 10 (with = 1) by analytically applying
the time evolution operator e
i

Ht
to (x, 0) term by term. Compare (x, t) to the resulting wave-
function obtained by numerically applying the Trotter expansion of e
i

H
10 times to the initial
superposition state.
16 Adiabatic Approximation
The goal of this section is to solve the time dependent Schr odinger equation,
i

t
=

H, (41)
for a time dependent Hamiltonian,

H =

2
2m

2
+ V (x, t), where the potential V (x, t) undergoes
signicant changes but in a very large time scale (e.g., a time scale much larger than the time
associated with state transitions).R2(496)
Since V(x,t) changes very slowly, we can solve the time independent Schr odinger equation at a
specic time t,

H(t

)
n
(x, t

) = E
n
(t

)
n
(x, t

).
Assuming that
n
t
0, since V(x,t) changes very slowly, we nd that the function,

n
(x, t) =
n
(x, t)e

t
0
En(t

)dt

,
is a good approximate solution to Eq. (41). In fact, it satises Eq. (41) exactly when
n
t
= 0.
Expanding the general solution (x, t) in the basis set
n
(x, t) we obtain:
(x, t) =

n
C
n
(t)
n
(x, t)e

t
0
En(t

)dt

,
and substituting this expression into Eq. (41) we obtain,
i

n
(

C
n

n
+ C
n

E
n
C
n

n
)e

t
0
En(t

)dt

n
C
n
E
n

n
e

t
0
En(t

)dt

,
36
where,

C
k
=

n
C
n
<
k
|

n
> e

t
0
dt

(En(t

)E
k
(t

))
. (42)
Note that,
H
t

n
+ H

n
=
E
n
t

n
+ E
n

n
,
then,
<
k
|
H
t
|
n
> + <
k
|H|

n
>=
E
k
t

kn
+ E
n
<
k
|

n
>,
since <
k
|H|

n
> = <

n
|H|
k
>

.
Furthermore, if k = n then,
<
k
|

n
>=
<
k
|
H
t
|
n
>
E
n
E
k
.
Substituting this expression into Eq. (42) we obtain,

C
k
= C
k
<
k
|

k
>

n=k
C
n
<
k
|
H
t
|
n
>
(E
n
E
k
)
e

t
0
dt

(En(t

)E
k
(t

))
.
Let us suppose that the system starts with C
n
(0) =
nj
, then solving by successive approximations
we obtain that for k = j:

C
k
=
<
k
|
H
t
|
j
>
(E
k
E
j
)
e

t
0
dt

(E
j
(t

)E
k
(t

))
.
Assuming that E
j
(t) and E
k
(t) are slowly varying functions in time:
C
k

<
k
|
H
t
|
j
>
i

(E
j
E
k
)
2
[e

(E
j
E
k
)t
e

(E
j
E
k
)t
0
],
since |e

(E
j
E
k
)t
e

(E
j
E
k
)t
0
| 2.
Therefore,
|C
k
|
2

4
2
| <
k
|
H
t
|
j
> |
2
(E
j
E
k
)
4
.
The system remains in the initially populated state at all times whenever
H
t
is sufciently small,

<
k
|
H
t
|
j
>

<<
(E
j
E
k
)
2

, (43)
even when such state undergoes signicant changes. This is the so-called adiabatic approximation.
It breaks down when E
j
E
k
because the inequality introduced by Eq. (43) can not be satised.
Mathematically, the condition that validates the adiabatic approximation can also be expressed in
terms of the frequency dened by the equation E
j
E
k
= h =
h

, (or the time period of the

light emitted with frequency ) as follows,
37

2
| <
k
|
H
t
|
j
> | << (E
j
E
k
).
38
17 Heisenberg Representation
Consider the eigenvalue problem,R4(124) R3(240)

H|
l
= E
l
|
l
, (44)
for an arbitrary state |
l
of a system (e.g., an atom, or molecule) expanded in a basis set {
j
}, as
follows:
|
l
=

j
C
(j)
l
|
j
, (45)
where C
(j)
l
=
j
|
l
, and
j
|
k
=
jk
. Substituting Eq. (45) into Eq. (44) we obtain:

H|
j
C
(j)
l
=

j
E
l
C
(j)
l
|
j
.
Applying functional
k
| to both sides of this equation we obtain,

k
|

H|
j
C
(j)
l
=

j
E
l

k
|
j
C
(j)
l
, (46)
where
k
|
j
=
kj
and k = 1, 2, ..., n.
Introducing the notation H
kj
=
k
|

H|
j
we obtain,
(k = 1)
(k = 2)
...
(k = n)
_

_
H
11
C
(1)
l
+ H
12
C
(2)
l
+ H
13
C
(3)
l
+ ... + H
1n
C
(n)
l
= E
l
C
(1)
l
+ 0C
(2)
l
+ ... + 0C
(n)
l
,
H
21
C
(1)
l
+ H
22
C
(2)
l
+ H
23
C
(3)
l
+ ... + H
2n
C
(n)
l
= 0C
(1)
l
+ E
l
C
(2)
l
+ ... + 0C
(n)
l
,
...
H
n1
C
(1)
l
+ H
n2
C
(2)
l
+ H
n3
C
(3)
l
+ ... + H
nn
C
(n)
l
= 0C
(1)
l
+ 0C
(2)
l
+ ... + E
l
C
(n)
l
,
(47)
that can be conveniently written in terms of matrices and vectors as follows,
_

_
H
11
H
12
... H
1n
H
21
H
22
... H
2n
...
H
n1
H
n2
... H
nn
_

_
_

_
C
(1)
l
C
(2)
l
...
C
(n)
l
_

_
=
_

_
E
l
0 ... 0
0 E
l
... 0
...
0 0 ... E
l
_

_
_

_
C
(1)
l
C
(2)
l
...
C
(n)
l
_

_
. (48)
This is the Heisenberg representation of the eigenvalue problem introduced by Eq. (44). According
to the Heisenberg representation, also called matrix representation, the ket |
l
is represented by
the vector C
l
, with components C
(j)
l
=
j
|
l
, with j = 1, ..., n, and the operator

H is represented
by the matrix H with elements H
jk
=
j
|

H|
k
.
The expectation value of the Hamiltonian,
|H| =

k
C
(k)
l

k
|

H|
j
C
(j)
l
,
39
can be written in the matrix representation as follows,
|H|
l
= C

l
HC
l
=
_
C
(1)
l
C
(2)
l
... C
(n)
l
_
_

_
H
11
H
12
... H
1n
H
21
H
22
... H
2n
...
H
n1
H
n2
... H
nn
_

_
_

_
C
(1)
l
C
(2)
l
...
C
(n)
l
_

_
.
Note:
(1) It is important to note that according to the matrix representation the ket-vector |
l
is repre-
sented by a column vector with components C
(j)
l
=
j
|
l
, and the bra-vector
l
| is represented
by a row vector with components C
(j)
l
.
(2) If an operator is hermitian (e.g.,

H) it is represented by a hermitian matrix (i.e., a matrix
where any two elements which are symmetric with respect to the principal diagonal are complex
conjugates of each other). The diagonal elements of a hermitian matrix are real numbers, therefore,
its eigenvalues are real.
(3) The eigenvalue problem has a non-trivial solution only when the determinant det[H

1E]
vanishes:
det[H

1E] = 0, where

1 is the unity matrix.
This equation has n roots, which are the eigenvalues of H.
(3) Finally, we note that the matrix of column eigenvectors C satisfy the equation, HC = EC,
where E is the diagonal matrix of eigenvalues:
_

_
H
11
H
12
... H
1n
H
21
H
22
... H
2n
...
H
n1
H
n2
... H
nn
_

_
_

_
C
(1)
1
C
(1)
2
C
(1)
n
C
(2)
1
C
(2)
2
C
(2)
n
... ... ... ...
C
(n)
1
C
(n)
2
C
(n)
n
_

_
=
_

_
E
1
0 ... 0
0 E
2
... 0
...
0 0 ... E
n
_

_
_

_
C
(1)
1
C
(1)
2
C
(1)
n
C
(2)
1
C
(2)
2
C
(2)
n
... ... ... ...
C
(n)
1
C
(n)
2
C
(n)
n
_

_
.
(49)
18 Two-Level Systems
There are many problems in Quantum Chemistry that can be modeled in terms of the two-level
Hamiltonian (i.e., a state-space with only two dimensions). Examples include electron transfer,
proton transfer, and isomerization reactions.
Consider two states |
1
> and |
2
>, of a system. Assume that these states have similar
energies, E
1
and E
2
, both of them well separated from all of the other energy levels of the system,

H
0
|
1
>= E
1
|
1
>,

H
0
|
2
>= E
2
|
2
> .
In the presence of a perturbation,
W =
_
0
0
_
,
40
the total Hamiltonian becomes H = H
0
+ W. Therefore, states |
1
> and |
2
> are no longer
eigenstates of the system.
The goal of this section is to compute the eigenstates of the system in the presence of the
perturbation W. The eigenvalue problem,
_
H
11
H
12
H
21
H
22
_
_
C
(1)
l
C
(2)
l
_
=
_
E
l
0
0 E
l
_
_
C
(1)
l
C
(2)
l
_
,
is solved by nding the roots of the characteristic equation, (H
11
E
l
)(H
22
E
l
) H
12
H
21
= 0.
The values of E
l
that satisfy such equation are,
E

l
=
(E
1
+ E
2
)
2

_
E
1
E
2
2
_
2
+
2
.
These eigenvalues E

l
can be represented as a function of the energy difference (E
1
E
2
), accord-
ing to the following diagram:
-
6
?
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H

.......................................................
.......................................................
E
m
+
E
m

E
m
=
1
2
(E
1
+ E
2
)
E
+
E
1
E
1
E
2
E
2 E

0
Note that E
1
and E
2
cross each other, but E

and E
+
repel each other. Having found the eigen-
values E

, we can obtain the eigenstates |

>= C
(1)

|
1
+C
(2)

|
2
by solving for C
(1)

and C
(2)

from the following equations:

C
(1)

(H
11
E

) + C
(2)

H
12
= 0,

2
j=1
C
(j)

C
(j)

= 1.
We see that in the presence of the perturbation the minimum energy state |

> is always more

stable than the minimum energy state of the unperturbed system.
Example 1. Resonance Structure
41

@
@
@
@
@
@

1

2
E
1
= E
2
= E
m

@
@
@
@
@
@

The coupling between the two states makes the linear combination of the two more stable than
the minimum energy state of the unperturbed system.
Example 2. Chemical Bond
u
H
+
r
e
u
H
+
|
2
>
u
H
+
r
e
u
H
+
|
1
>
The state of the system that involves a linear combination of these two states is more stable than
E
m
because <
1
|H|
2
>= 0.
Time Evolution
Consider a two level system described by the Hamiltonian H = H
0
+ W, with H
0
|
1
>= E
1
|

1
>. Assume that the system is initially prepared in state | (0) >=|
1
>. Due to the presence
of the perturbation W, state |
1
> is not a stationary state. Therefore, the initial state evolves in
time according to the time-dependent Schr odinger Equation,
i
| >
t
= (H
0
+ W) | >,
and becomes a linear superposition of states |
1
> and |
2
>,
|(t) >= C
1
(t)|
1
> +C
2
(t)|
2
> .
42
State | (t) > can be expanded in terms of the eigenstates |

> as follows,
|(t) >= C
+
(t)|
+
> +C

(t)|

>,
where the expansion coefcients C

(t) evolve in time according to the following equations,

i
C
+
(t)
t
= E
+
C
+
(t),
i
C

(t)
t
= E

(t).
Therefore, state |(t) > can be written in terms of |

> as follows,
|(t) >= C
+
(0)e

E
+
t
|
+
> +C

(0)e

t
|

> .
The probability amplitude of nding the system in state |
2
> at time t is,
P
12
(t) = | <
2
|(t) > |
2
= C
2
(t)

C
2
(t),
which can also be written as follows,
P
12
(t) = |C
2+
C
+
(0)|
2
+|C
2
C

(0)|
2
+ 2Re[C

2+
C

+
(0)C
2
C

(0)e

(E

E
+
)t
],
where C
2
=<
2
|

>. The following diagram represents P

12
(t) as a function of time:
Rabi Oscillations
6
-
P
12
(t)
0 t

E
+
E

The frequency = (E
+
E

)/() is called Rabi Frequency. It is observed, e.g., in the

absorption spectrum of H
+
2
(see Example 2). It corresponds to the frequency of the oscillating
dipole moment which uctuates according to the electronic congurations of |
1
> and |
2
>,
respectively. The oscillating dipole moment exchanges energy with an external electromagnetic
eld of its own characteristic frequency and, therefore, it is observed in the absorption spectrum of
the system.
43
19 Harmonic Oscillator
Many physical systems, including molecules with congurations near their equilibrium positions,
can be described (at least approximately) by the Hamiltonian of the harmonic oscillator:R4(483)
R1(62) click

H =

P
2
2m
+
1
2
m
2
x
2
.
In order to nd the eigenfunctions of

H we introduce two operators called creation a
+
and annihi-
lation a, which are dened as follows:
a
+

2
( x i p), and a
1

2
( x + i p), where x = x
_
m

, and p =
p

m
.
Using these denitions of a
+
and a, we can write

H as follows,

H = ( a
+
a +
1
2
).
Introducing the number operator

N, dened in terms of a
+
and a as follows,

N a
+
a,
we obtain that the Hamiltonian of the Harmonic Oscillator can be written as follows,

H = (

N + 1/2).
19.1 Exercise 15
Show that if

is an eigenfunction of

H with eigenvalue E

, then

is an eigenfunction of

N
with eigenvalue =
E

1
2
. Mathematically, if

H|

>= E

>, then

N|

>= |

>, with
=
E

1
2
.
Theorem I
The eigenvalues of

N are greater or equal to zero, i.e., 0.
Proof:
_
dx| < x| a|

> |
2
0,
<

| a
+
a|

> 0,
<

> 0.
As a consequence: a|
0
>= 0,
1

2
[ x
_
m

+ i
p

m
]|
0
>= 0,
p = i

x
,
x
0
(x) +

m

0
(x)
x
= 0,
ln
0
(x) =
m

xx,

0
(x) = A exp(
m
2
x
2
),
where A =
4
_
m

. The wave function

0
(x) is the eigenfunction of

N with = 0 (i.e., the ground
state wave function because 0).
44