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

1.

matrix elements

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

perturbation

One-dimensional anharmonic oscillator:

ψ n+3 |x 3 |ψ n =

ψ n+1 |x 3 |ψ n

ψ n1 |x 3 |ψ n

ψ n3 |x 3 |ψ n

=

=

=

(n + 3)(n + 2)(n + 1)

8

3 n + 1

2

3

2

,

3 n

2

3

2

,

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:

n (x) = n + 1 ψ n+1 (x) + n ψ n1 (x).

2

2

Employing Eq. (1.1), we obtain

x 2 ψ n (x)

=

2 (n + 2)(n + 1)ψ n+2 (x) + n +

1

1 ψ n (x) +
2

1

2 n(n 1)ψ n2 (x).

(1.1)

(1.2)

Employing Eqs. (1.2) and (1.1), we obtain

x 3 ψ n (x)

=

=

=

xx 2 ψ n (x)

2 (n + 2)(n + 1)n+2 (x) + n +

1

1 n (x) +
2

1

2 n(n 1)n2 (x)

(n + 3)(n + 2)(n + 1)

8

ψ n+3 (x) + 3 n + 1

2

3/2 ψ n+1 (x)

+3 n

2

3/2 ψ n1 (x) + n(n 1)(n 2)

8

ψ n3 (x).

(1.3)

The energy eigenfunctions ψ n (x) are orthonormal. Therefore, by multiplying both sides by ψ n+3 (x) and integrating from minus inﬁnity to inﬁnity, we obtain

ψ n+3 |x 3 |ψ n =

(n + 3)(n + 2)(n + 1)

8

1

.

(1.4)

Similarly we obtain

ψ n+1 |x 3 |ψ n

ψ n1 |x 3 |ψ n

ψ n3 |x 3 |ψ n

=

=

=

3 n + 1

2

3/2

3 n

2

3/2 ,

,

n(n 1)(n 2)

8

2

.

(1.5)

perturbative

treatment

Let us consider an anharmonic oscillator in which the perturbation is of the form H 1 = σ ωx 3 . First, show that the energy levels are (to the second order in σ)

2.

One-dimensional anharmonic oscillator:

E n = (n + 1

2 ) ω σ 2 ω 15 (n + 2 ) 2 +

4

1

16 .

7

Then, show that the energy diﬀerence

E n E n1 = 1 15 σ 2 n ω.

2

Finally, determine the energy eigenfunctions to the ﬁrst order in σ. This topic is discussed in the lecture notes section 17.2.3.

Solution

The energy levels are, to the second order in σ, [cf. Eq. (144)]

E n

=

E

(0)

n

+ ψ

(0)

n

|H 1 |ψ

(0)

n

+

m

=n

|

ψ (0) |H 1 |ψ (0) | 2

m

n

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 1/2) ω, where n ∈ {0, 1, · · · }. Using these results, we obtain

= (n +

(0)

n

E n

=

=

=

=

E

(0)

n

+

|

(0)

ψ n3 |H 1 |ψ

(0)

n

| 2

E

(0)

n

E

(0)

n3

+

|

(0)

ψ n1 |H 1 |ψ

(0)

n

| 2

E

(0)

n

E

(0)

n1

+

(0)

| ψ n+1 |H 1 |ψ

(0)

n

| 2

E

(0)

n

E

(0)

n+1

n +

+

|

ψ

(0)

n+3 |H 1 |ψ (0)

n

| 2

E

(0)

n

E (0)

n+3

1 ω + σ 2 ω n(n 1)(n 2)

2

 + 9n 3 − 9(n + 1) 3 24 8 8

n +

(n + 3)(n + 2)(n + 1)

24

1

2 ω + σ 2 ω 24 (n 3 3n 2 + 2n) + 9

1

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

24 (n 3 + 6n 2 + 11n + 6)

1

n + 1 2 ω σ 2 ω 15 (n + 1

4

2 ) 2 + 16 .

7

The energy diﬀerence

E n E n1

=

=

(n +

1

2 ) ω σ 2 ω 15 (n + 1

4

2 ) 2 +

16

7

(n 1 + 1 2 ) ω + σ 2 ω 15 (n 1 + 1

4

2 ) 2 +

1 15 σ 2 n ω.

2

16

7

(2.2)

(2.3)

3

The nth energy eigenfunction is, to the ﬁrst order in σ, [cf. Eq. (144)]

ψ n

=

=

=

ψ

ψ

ψ

(0)

n

(0)

n

(0)

n

+

+

+

+

m

=n

ψ

(0)

m

|H 1 |ψ E

(0)

n

(0)

m

(0)

n

E

ψ

(0)

m

σ ψ n3 |x 3 |ψ

3

σ ψ n+1 |x 3 |ψ

(0)

(0)

(0)

n

ψ n3 + σ ψ n1 |x 3 |ψ

ψ

(0)

n+1 σ

3

(0)

ψ n+3 |x 3 |ψ

(0)

(0)

(0)

n

(0) ψ (0)

n

n1

(0) ψ (0)

n

n+3

σ

1 n(n 1)(n 2)

3

3 n + 1

ψ

(0)

(0)

n+1

n3 + 3 n

2

3/2 ψ

(0)

n1

2

8

3/2

ψ

1 (n + 3)(n + 2)(n + 1)

3

8

4

ψ n+3 .

(0)

(2.4)

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

2

A

6 1s| r

3

6

12a 0 × Ry.

|1s

2

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

=

A x 2

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 .

Substitution Eq. (3.2) into Eq. (3.1) yields

C

=

e 4 1s 1s; 1s|x 2

2E

A x 2

B |1s; 1s + 1s; 1s|y

2

A y

2

B |1s; 1s + 4 1s; 1s|z

2

A z

2

B |1s; 1s

+2 1s; 1s|x A x B y A y B |1s; 1s

4 1s; 1s|x A x B z A z B |1s;

1s

4 1s; 1s|y A y B z A z B |1s; 1s .

(3.2)

(3.3)

The wave function of the state 1s is (cf. p. 148)

ψ 100 (r) =

1 π e r .

(3.4)

The Cartesian and spherical coordinates of electron A are related by

  x A

y A

=

=

r A sin θ A cos ϕ A ,

r A sin θ A sin ϕ A ,

r

z A

=

A

cos θ 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

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Eqs. (3.4) and (3.5), we obtain

1s; 1s|x A x B y A y B |1s; 1s

=

=

=

R 3 R 3 ψ 100 (r A ) ψ 100 (r B ) x A x B y A y B

×ψ 100 (r A )ψ 100 (r B ) dV A dV B

2

π

×

1

e 2r A r 4

0

e 2r B r 4

0

A dr A

B dr B

0

0

π

π

sin 3 θ A A

sin 3 θ B B

2π

cos ϕ A sin ϕ A

0

2π

cos ϕ B sin ϕ B

0

 =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 + 4 1s; 1s|z

2

A z

2

B |1s; 1s .

(3.7)

The ﬁrst matrix element inside the brackets,

1s; 1s|x 2

A x 2

B |1s; 1s

 = = R 3 R 3 ψ 100 (r A ) ∗ ψ 100 (r B ) ∗ x 2 A x 2 B ψ 100 (r A )ψ 100 (r B ) dV A dV B R 3 ψ 100 (r A ) ∗ x 2 A ψ 100 (r A ) dV A R 3 ψ 100 (r B ) ∗ x 2 B ψ 100 (r B )dV B = 1s|x 2 |1s = 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 + 4 1s|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 6 1s|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 ψ 100 (r) r 2 ψ 100 (r) dV

π

1

0

r 4 e 2r dr π sin θ dθ 2π

0

0

=4π

=

4 r 4 e 2r dr

0

= 3,

6

(3.11)

where the last equality follows from integration by parts. Writing the Bohr radius a 0 explicitly, we obtain

1s|r 2 |1s = 3a 0 .

2

(3.12)

The shorthand e 2 is deﬁned 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

0 2

1

4π

a

0

2

q

2

4π 0

a

0

=2 Ry

4a 0 × (Ry) 2 .

2

2

(3.13)

Rydberg is deﬁned 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

6

C = 12a 0 × Ry.

7

(3.15)

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 ﬁlled up to energy E F = 1 Ry. Estimate the strength of the harmonic potential, V 0 = ω.

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 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 ) ω.

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)

1

Since we are now, however, dealing with spin– 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 speciﬁed by the spatial wave function alone, but by the spin also. In the case of spin– 2 particles, the spin can obtain two diﬀerent values.

1

8

In the second column of Table 1, the degeneracies of the ﬁrst 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 ﬁlled 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

Consequently,

E F

=

=

ω =

E 5

5 + 3 ω.

2

2

13 Ry.

9

(4.5)

(4.6)

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 diﬀerence that the charge of the nucleus is Ze, where Z is the number of protons in the nucleus. Thus the time-independent Schr¨odinger equation for each electron reads (cf. p. 144)

2

2m

2

r ψ(r)

1

4π 0

Ze 2

r

ψ(r) = (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 (cf. pp. 144-145). That is, let us make the substitutions

0 2 )

We obtain

1

4π 0

ψ(r)

r

E

Ze 2

a

0

=

=

=

=

u(r ),

a Z 0 r ,

where r =

2ma Z 2 2 E , 2 Z 2

2

0

2ma

2

0

.

r

a 0 /Z ,

2

r u(r ) 2 2ma Z 2 2

1

2

0

r

u(r ) = Z 2 2 E u(r ).

2ma

2m 2

2

0

(5.2)

(5.3)

As we cancel out common factors and rearrange, we obtain

r u(r ) + 2 Z 2

2

a

2

0

r

+ Z 2

1

a

2

0

E u(r ) = 0.

(5.4)

Let us evaluate the ﬁrst 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

Z

∂u

a 0

∂x .

10

|| x ∂x

1

a 0 /Z

=

(5.5)

As we employ the previous equation and the fact that the order of partial diﬀerentiations can be swapped, we obtain

2 u

∂x 2

=

=

Z

∂u

∂x ∂x

a

Z 2 2 u

0

a

2

0

∂x 2 .

(5.6)

This leads us to see that

r u(r ) = Z 2 2 u(r ),

2

a

2

0

(5.7)

where 2 =

2 . Indeed, we have now evaluated the ﬁrst term at

the left-hand side of Eq. (5.4). Substituting and cancelling out common factors, we obtain

∂x 2 +

2

∂y 2 +

2

2

∂z

2 u(r ) +

+ E u(r ) = 0.

2

r

(5.8)

We note that this is the lecture notes Eq. (132) with the exceptions that ψ 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 2 ,

n

(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 ﬁrst 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.

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