763312A QUANTUM MECHANICS I - solution set 13 - autumn 2012

1. One-dimensional anharmonic oscillator: perturbation

matrix elements
Consider a one-dimensional anharmonic oscillator. Let the perturbation be of
the form H
1
= x
3
. Calculate the matrix elements

n+3
|x
3
|
n
=
_
(n + 3)(n + 2)(n + 1)
8
,

n+1
|x
3
|
n
= 3
_
n + 1
2
_3
2
,

n1
|x
3
|
n
= 3
_
n
2
_3
2
,

n3
|x
3
|
n
=
_
n(n 1)(n 2)
8
.
Solution
In the lecture notes section 17.2 we derived a recurrence relation for the har-
monic oscillator energy eigenfunctions. Let us repeat it here:
x
n
(x) =
_
n + 1
2

n+1
(x) +
_
n
2

n1
(x). (1.1)
Employing Eq. (1.1), we obtain
x
2
n(x) =
1
2
_
(n + 2)(n + 1)n+2(x) +
_
n +
1
2
_
n(x) +
1
2
_
n(n 1)n2(x). (1.2)
Employing Eqs. (1.2) and (1.1), we obtain
x
3
n(x) = xx
2
n(x)
=
1
2
_
(n + 2)(n + 1)xn+2(x) +
_
n +
1
2
_
xn(x) +
1
2
_
n(n 1)xn2(x)
=

(n + 3)(n + 2)(n + 1)
8
n+3(x) + 3
_
n + 1
2
_
3/2
n+1(x)
+3
_
n
2
_
3/2
n1(x) +

n(n 1)(n 2)
8
n3(x). (1.3)
The energy eigenfunctions
n
(x) are orthonormal. Therefore, by multiplying
both sides by
n+3
(x) and integrating from minus innity to innity, we obtain

n+3
|x
3
|
n
=
_
(n + 3)(n + 2)(n + 1)
8
. (1.4)
1
Similarly we obtain

n+1
|x
3
|
n
= 3
_
n + 1
2
_
3/2
,

n1
|x
3
|
n
= 3
_
n
2
_
3/2
,

n3
|x
3
|
n
=
_
n(n 1)(n 2)
8
. (1.5)
2
2. One-dimensional anharmonic oscillator: perturbative
treatment
Let us consider an anharmonic oscillator in which the perturbation is of the
form H
1
= x
3
. First, show that the energy levels are (to the second order
in )
E
n
= (n +
1
2
)
2

_
15
4
(n +
1
2
)
2
+
7
16
_
.
Then, show that the energy dierence
E
n
E
n1
=
_
1
15
2

2
n
_
.
Finally, determine the energy eigenfunctions to the rst order in .
This topic is discussed in the lecture notes section 17.2.3.
Solution
The energy levels are, to the second order in , [cf. Eq. (144)]
E
n
= E
(0)
n
+
(0)
n
|H
1
|
(0)
n
+

m=n
|
(0)
m
|H
1
|
(0)
n
|
2
E
(0)
n
E
(0)
m
. (2.1)
In the previous problem, we calculated the values of all nonzero matrix elements.
Moreover, we know that the harmonic oscillator energy levels are E
(0)
n
= (n +
1/2), where n {0, 1, }. Using these results, we obtain
En = E
(0)
n
+
|
(0)
n3
|H
1
|
(0)
n
|
2
E
(0)
n
E
(0)
n3
+
|
(0)
n1
|H
1
|
(0)
n
|
2
E
(0)
n
E
(0)
n1
+
|
(0)
n+1
|H
1
|
(0)
n
|
2
E
(0)
n
E
(0)
n+1
+
|
(0)
n+3
|H
1
|
(0)
n
|
2
E
(0)
n
E
(0)
n+3
=
_
n +
1
2
_
+
2

_
n(n 1)(n 2)
24
+
9n
3
8

9(n + 1)
3
8

(n + 3)(n + 2)(n + 1)
24
_
=
_
n +
1
2
_
+
2

_
1
24
(n
3
3n
2
+ 2n) +
9
8
n
3

9
8
(n
3
+ 3n
2
+n + 1)

1
24
(n
3
+ 6n
2
+ 11n + 6)
_
=
_
n +
1
2
_

2

_
15
4
(n +
1
2
)
2
+
7
16
_
. (2.2)
The energy dierence
En E
n1
= (n +
1
2
)
2

_
15
4
(n +
1
2
)
2
+
7
16
_
(n 1 +
1
2
) +
2

_
15
4
(n 1 +
1
2
)
2
+
7
16
_
=
_
1
15
2

2
n
_
. (2.3)
3
The nth energy eigenfunction is, to the rst order in , [cf. Eq. (144)]
n =
(0)
n
+

m=n

(0)
m
|H
1
|
(0)
n

E
(0)
n
E
(0)
m

(0)
m
=
(0)
n
+

3

(0)
n3
|x
3
|
(0)
n

(0)
n3
+
(0)
n1
|x
3
|
(0)
n

(0)
n1
+
(0)
n+1
|x
3
|
(0)
n

(0)
n+1


3

(0)
n+3
|x
3
|
(0)
n

(0)
n+3
=
(0)
n
+
_
1
3
_
n(n 1)(n 2)
8

(0)
n3
+ 3
_
n
2
_
3/2

(0)
n1
3
_
n + 1
2
_
3/2

(0)
n+1

1
3
_
(n + 3)(n + 2)(n + 1)
8

(0)
n+3
_
. (2.4)
4
3. van der Waals constant
Calculate the van der Waals constant
C =
e
4
2E
1s
1s; 1s|(x
A
x
B
+y
A
y
B
2z
A
z
B
)
2
|1s; 1s
=
e
4
2E
1s
6

1s|
r
2
A
3
|1s

2
= 12a
6
0
Ry.
Solution
The van der Waals force between two hydrogen atoms is discussed in the lecture
notes section 17.2.4. Here we begin from the result
C =
e
4
2E
1s
1s; 1s|(x
A
x
B
+y
A
y
B
2z
A
z
B
)
2
|1s; 1s. (3.1)
Since the position operators commute with each other,
(x
A
x
B
+y
A
y
B
2z
A
z
B
)
2
= x
2
A
x
2
B
+y
2
A
y
2
B
+ 4z
2
A
z
2
B
+ 2x
A
x
B
y
A
y
B
4x
A
x
B
z
A
z
B
4y
A
y
B
z
A
z
B
. (3.2)
Substitution Eq. (3.2) into Eq. (3.1) yields
C =
e
4
2E
1s
_
1s; 1s|x
2
A
x
2
B
|1s; 1s + 1s; 1s|y
2
A
y
2
B
|1s; 1s + 41s; 1s|z
2
A
z
2
B
|1s; 1s
+21s; 1s|x
A
x
B
y
A
y
B
|1s; 1s 41s; 1s|x
A
x
B
z
A
z
B
|1s; 1s
41s; 1s|y
A
y
B
z
A
z
B
|1s; 1s
_
. (3.3)
The wave function of the state 1s is (cf. p. 148)

100
(r) =
1

e
r
. (3.4)
The Cartesian and spherical coordinates of electron A are related by
_
_
_
x
A
= r
A
sin
A
cos
A
,
y
A
= r
A
sin
A
sin
A
,
z
A
= r
A
cos
A
.
(3.5)
Naturally, the Cartesian and spherical coordinates of electron B are related in
a similar manner.
Since we know that the state 1s is spherically symmetric, we have the intu-
ition that the last three matrix elements at the right-hand side of Eq. (3.3) are
zero. However, let us also calculate the third last matrix element. Employing
5
Eqs. (3.4) and (3.5), we obtain
1s; 1s|x
A
x
B
y
A
y
B
|1s; 1s =
_
R
3
_
R
3
100(r
A
)

100(r
B
)

x
A
x
B
y
A
y
B
100(r
A
)100(r
B
) dV
A
dV
B
=
1

2
_

0
e
2r
A
r
4
A
dr
A
_

0
sin
3

A
d
A
_
2
0
cos
A
sin
A
d

_

0
e
2r
B
r
4
B
dr
B
_

0
sin
3

B
d
B
_
2
0
cos
B
sin
B
d
.
=0
= 0. (3.6)
Indeed, the third last matrix element vanishes as we expected. Similarly we can
show that both the second last and the last matrix element indeed vanish. Thus
we now have the result
C =
e
4
2E
1s
_
1s; 1s|x
2
A
x
2
B
|1s; 1s + 1s; 1s|y
2
A
y
2
B
|1s; 1s + 41s; 1s|z
2
A
z
2
B
|1s; 1s
_
. (3.7)
The rst matrix element inside the brackets,
1s; 1s|x
2
A
x
2
B
|1s; 1s =
_
R
3
_
R
3
100(r
A
)

100(r
B
)

x
2
A
x
2
B
100(r
A
)100(r
B
) dV
A
dV
B
=
_
R
3
100(r
A
)

x
2
A
100(r
A
) dV
A
.
=1s|x
2
|1s
_
R
3
100(r
B
)

x
2
B
100(r
B
)dV
B
.
=1s|x
2
|1s
= 1s|x
2
|1s
2
. (3.8)
For the second last and the last matrix element we obtain similar results. Thus
we have the result
C =
e
4
2E
1s
_
1s|x
2
|1s
2
+ 1s|y
2
|1s
2
+ 41s|z
2
|1s
2
_
. (3.9)
Since the state 1s is spherically symmetric, we have the intuition that the matrix
elements at the right-hand side of Eq. (3.9) are equal (we could verify this by a
simple calculation). Application of this fact yields
C =
e
4
2E
1s
61s|r
2
/3|1s
2
=
e
4
3E
1s
1s|r
2
|1s
2
, (3.10)
where r
2
= x
2
+y
2
+z
2
. On the other hand,
1s|r
2
|1s =
_
R
3

100
(r)

r
2

100
(r) dV
=
1

_

0
r
4
e
2r
dr
_

0
sin d
_
2
0
d
. .
=4
= 4
_

0
r
4
e
2r
dr
= 3, (3.11)
6
where the last equality follows from integration by parts. Writing the Bohr
radius a
0
explicitly, we obtain
1s|r
2
|1s = 3a
2
0
. (3.12)
The shorthand e
2
is dened on the lecture notes p. 162. We wish to express it
in terms of Rydbergs and the Bohr radius. We obtain (cf. pp. 144-145)
e
4
=
_
q
2
4
0
_
2
= a
2
0
_
1
4
0
q
2
a
0
. .
=2 Ry
_
2
= 4a
2
0
(Ry)
2
. (3.13)
Rydberg is dened as the ionization energy of hydrogen. Thus
E
1s
= 1 Ry. (3.14)
As we substitute Eqs. (3.12) - (3.14) into Eq. (3.10), we obtain
C = 12a
6
0
Ry. (3.15)
7
4. A fermion system
Consider a system composed of noninteracting spin
1
2
fermions in a three-
dimensional harmonic oscillator potential. First, describe the shell structure of
the system. Then, suppose that there are a total of 100 particles in the system
and that all the energy states of the system are lled up to energy E
F
= 1 Ry.
Estimate the strength of the harmonic potential, V
0
= .
Solution
E
N
degeneracy total
E
0
2 2
E
1
6 8
E
2
12 20
E
3
20 40
E
4
30 70
E
5
42 112
E
6
56 168
.
.
.
.
.
.
.
.
.
Table 1: Shell structure
Since we assume that the fermions do not interact with each other, the harmonic
oscillator potential
V (r) =
1
2
m
2
r
2
(4.1)
is the potential each fermion experiences. Therefore the energy levels of each
fermion are (cf. p. 130)
E
N
= (N +
3
2
). (4.2)
For spinless particles, the degeneracy of level E
N
is (cf. p. 130)
f
N
=
1
2
(N + 1)(N + 2). (4.3)
Since we are now, however, dealing with spin
1
2
particles, the degeneracy of
level E
N
is
1
g
N
= 2f
N
= (N + 1)(N + 2). (4.4)
1
The state of a fermion is not specied by the spatial wave function alone, but by the spin
also. In the case of spin
1
2
particles, the spin can obtain two dierent values.
8
In the second column of Table 1, the degeneracies of the rst seven energy levels
are given. In the third column, the total number of states, up to the level in
question, is given.
Let us suppose that there are a total of 100 particles in the system and that
all the energy states of the system are lled up to the energy E
F
= 1 Ry. Now,
according to Table 1, the sixth shell is the last shell having nonzero occupation
number. Thus we conclude that
E
F
= E
5
=
_
5 +
3
2
_
. (4.5)
Consequently,
=
2
13
Ry. (4.6)
9
5. Binding energies in hydrogen, helium, and lithium
Consider a hydrogen, a helium and a lithium atom and assume that there is no
Coulomb interaction between the electrons. Calculate the binding energies of
the outmost electrons. Does this model give the correct shell structure for these
atoms, or for heavier atoms?
Since we assume that there is no Coulomb interaction between the electrons, the
shell structures of all the three atoms can be solved in a similar manner.
Solution
It is well-known that when the hydrogen atom is in its ground state, the binding
energy of the electron is 13.6 eV. What comes to the heavier elements, we begin
from the assumption that there is no Coulomb interaction between the electrons.
Consequently, on part of each electron, the system is like the hydrogen atom
with the dierence that the charge of the nucleus is Ze, where Z is the number
of protons in the nucleus. Thus the time-independent Schrodinger equation for
each electron reads (cf. p. 144)

2
2m

2
r
(r)
1
4
0
Ze
2
r
(r) = E(r). (5.1)
Let us express the quantities in natural units with the exceptions that we now
measure length in multiples of a
0
/Z and energy in multiples of Z
2

2
/(2ma
2
0
)
(cf. pp. 144-145). That is, let us make the substitutions
(r) = u(r

), where r

=
r
a
0
/Z
,
r =
a
0
Z
r

,
E =
Z
2

2
2ma
2
0
E

,
1
4
0
Ze
2
a
0
= 2
Z
2
2ma
2
0
. (5.2)
We obtain

2
2m

2
r
u(r

) 2
Z
2

2
2ma
2
0
1
r

u(r

) =
Z
2

2
2ma
2
0
E

u(r

). (5.3)
As we cancel out common factors and rearrange, we obtain

2
r
u(r

) +
_
2
Z
2
a
2
0
1
r

+
Z
2
a
2
0
E

_
u(r

) = 0. (5.4)
Let us evaluate the rst term at the left-hand side. Firstly, as we use the
notation r

= (x

, y

, z

) and apply the chain rule, we obtain

u
x
=
u
x

x
||
x

x
=
1
a
0
/Z
=
Z
a
0
u
x

. (5.5)
10
As we employ the previous equation and the fact that the order of partial
dierentiations can be swapped, we obtain

2
u
x
2
=
Z
a
0

u
x
=
Z
2
a
2
0

2
u
x

2
. (5.6)
This leads us to see that

2
r
u(r

) =
Z
2
a
2
0

2
u(r

), (5.7)
where
2
=

2
x
2
+

2
y
2
+

2
z
2
. Indeed, we have now evaluated the rst term at
the left-hand side of Eq. (5.4). Substituting and cancelling out common factors,
we obtain

2
u(r

) +
_
2
r

+E

_
u(r

) = 0. (5.8)
We note that this is the lecture notes Eq. (132) with the exceptions that has
been denoted by u, r by r

and E by E

. Like in the lecture notes, we obtain

the result that the energy levels are
E

n
=
1
n
2
, (5.9)
where n {1, 2, 3, }. However, due to our choice of units, energy is now
measured in multiples of Z
2
Rydbergs (cf. Eq. (5.2) and pp. 144-145). For
example, the energies of the rst and the second level are Z
2
Rydbergs and
Z
2
/4 Rydbergs, respectively.
When we do not take the spin into account, we obtain the result that the
energy level E

n
is n
2
-fold degenerate (cf. p. 147). Taking the spin into account
doubles the degeneracy of each level. Thus, when a helium atom is in its ground
state, its electrons occupy the lowest energy level. Their binding energy
E
B
= E
1
2
2
Rydbergs
= 4 Rydbergs. (5.10)
When a lithium atom is in its ground state, the outmost of its electrons occupies
the second energy level (lithium has three electrons and up to two electrons can
occupy the lowest energy level simultaneously). Thus the binding energy of the
outmost electron is
E
B
= E
2
3
2
Rydbergs
=
9
4
Rydbergs. (5.11)
This model does not give the correct shell structure for helium or any element
heavier than it. This is due to the fact that neglecting the Coulomb interaction
between the electrons is a crude approximation.
11