SM358 Exam 2007 Answers to Part 1

Chris B Clarke

20/9/12

These answers were taken from the screencasts by tutors Stan Zochowski and Gillian
Stansfield . Any errors here are mine!

QUESTION 1
A de Broglie wave function takes the form :
dB ( x ,t )=Ae i (Bx Ct)
where B = 1.90 x 1020 m1 and C = 2.86 x 1016 s1 .
Name the physical quantities represented by B and C and use these quantities to evaluate
the energy and momentum associated with the de Broglie wave.
From the 1st page of the Equations booklet:
B is the wave-number k

C is the angular frequency

The energy is

E = h k = 1.061034 2.861016 = 3.031018 Joules

The momentum is

34
20
14
1
p x = h = 1.0610 1.9010 = 2.0110 kg ms

QUESTION 2
(a) State Borns rule as it applies to the wave function (x, t) of a particle in one
dimension. Explain why this rule requires the wave function to be normalized.
Born's rule states that the probability of finding the particle at time t in a small interval t,
centred on position x is:
2
Probability = ( x , t) x
We know that the particle will be found somewhere along the x-axis, so we need the
normalisation function:

2
( x , t) x = 1
(b) At t = 0, a wave function takes the form

( x , 0)= N
0

for a / 2 x a /2
elsewhere

where N and a are real positive constants. Use the normalization condition to express N in
terms of a.
a/2

Using the normalization condition:

a / 2 N

But N is a constant:

N a / 2 1 dx = 1

x =1

a/2

Carry out the integration:

2

a/2

N [ x ]a / 2= 1

[ ( )]

a
a
N
2
2
2

a/2

=1

a /2

N a = 1
Therefore

N=

1
a

QUESTION 3
At time t = 0, the wave function describing the state of a system takes the form
(x , 0) = C 1 ( x) 2C 2 ( x)
where 1 (x) and 2 (x) are normalized energy eigenfunctions for the system with
eigenvalues E1 and E2 respectively (E1 E2 ).
(a) Using the coefficient rule, or otherwise, find a suitable value of the normalization
constant C.
We are told that the energy eigenfunctions are normalized, so we can use the coefficient
rule.
2
2
C + 2 C = 1
for normalization
Rearranging:

C + 4 C = 1
2

5 C = 1

so

C =

1
5

Hence, as we choose C to be both real and positive:

C=

1
5

(b) What are the possible values of an energy measurement taken at t = 0, and what are
the probabilities of these values?
The possible energies are E1 and E2.
The probability of the energy measurement being E 1 is:

1( x) = C =

1
5

The probability of the energy measurement being E 2 is:

2 C

To check:

2 (x ) = 2 C =

1 4 5
+ = =1
5 5 5

4
5

QUESTION 4
(a) A particle in a harmonic oscillator potential energy well has a position coordinate x that
is represented by the operator
a
x =
( A + A )
2
where a is a constant and A and A are lowering and raising operators for the harmonic
oscillator. Use these operators to show that the expectation value of x is equal to zero in
the ground state of the harmonic oscillator.
The expectation value of x is given by:

x = 0 ( x) x 0 ( x) dx
Substituting the given operator, we obtain:

x = 0 ( x) a ( A + A ) 0 ( x ) dx

( 2

Now, A and 0 (x) are orthogonal, so A 0 ( x ) = 0

A 1 ( x) = 1 1 ( x ) = 1 (x )

Also,
Thus,

x =
Therefore,

a
2

0 ( x) 1 ( x) dx

x = 0

but

and

are orthonormal.

as required.

(b) Obtain the same result without using lowering and raising operators, but using the fact
that the ground-state energy eigenfunction of a harmonic oscillator is an even function of
x.
Looking at the expectation value we have:

x = 0 ( x ) x 0 ( x) dx

= even function odd function even function dx

= odd function dx = 0
Therefore,

x = 0

as required.

QUESTION 5
(a) Use Dirac notation to define what is meant by saying that an operator O is Hermitian.
is Hermitian if it obeys: f O
g = O
f g
The operator O

(b) State one important property of the eigenvalues and one important property of the
eigenfunctions of Hermitian operators.
The Eigenvalues of hermitian operators are real.
The Eigenfunctions of hermitian operators are orthogonal.
(c) Given that

0 for any normalized , show that

B 2

for any normalized , provided that B is Hermitian.

The given term can be rearranged:

B 2 = B

= B B
Now, let B be any function 'q'.
Substituting into the above term, we obtain:

B B = q q 0
as required.

QUESTION 6
(a) Verify that eim is an eigenfunction of the angular momentum operator

LZ = i h
and show that the corresponding eigenvalue is m h .
Using the given operator, we obtain:
im
im
LZ e = i h e

= i h ( i m ) ei m = i 2 h m e i m
= m h ei m
We have recovered the original function eim, so it must be an eigenfunction of the given
operator LZ .
Also, eim is multiplied by m h so this is the eigenvalue.
(b) What are the possible values of m?
The values of m are 0, 1, 2, ...
(c) Explain in one or two sentences why these are the only possible values of m.
For the eigenfunction, eim, we want it to be a single valued function.
So,

e i m = e i m ( + 2 ) = e i m e i m 2

However, for e i m 2 to equal 1, m must be an integer value: 0, 1, 2, ...

Therefore, these are the only possible values of m.

QUESTION 7
This question is concerned with the expectation value of a time-independent observable X
in a given system. The operator corresponding to X is denoted by X , and does not
depend explicitly on time.
(a) Use the sandwich rule to show that the expectation value <X> remains constant in time
if the system is in a stationary state, described by a wave function of the form

(x , t)= ( x )e i E t / h

X = ( x ,t ) X ( x ,t ) dx

The sandwich rule is:

We are given the wave function, so we can substitute to obtain:

X = ( x) e+i E t /h X ( x) e i E t /h dx

Carrying out the integration, we obtain:

X = e+i E t / h e i E t /h ( x) X ( x) dx

as we are integrating w.r.t x

= e 0 (x ) X ( x ) dx = ( x ) X (x ) dx
The time-dependent factor has disappeared, so the expectation value will remain constant
in time.
(b) Use the generalized Ehrenfest theorem to show that the expectation value <X>
remains constant in time if the operator X commutes with the Hamiltonian operator H
of the system.
In this context, the generalized Ehrenfest theorem is:
dX
1
=
[ X , H ]
dt
i h
Now, as X commutes with H , the above becomes:
dX
1
=
[ X H H X ] = 0
dt
i h
Thus, the rate of change of the expectation value of X is zero, and it will remain constant in
time.

QUESTION 8
In the BB84 protocol, Alice and Bob share a pair of orthonormal bases to prepare and
detect photon polarizations.
(a) What is the angle between these two bases? If Alice prepares a photon to be vertically
polarized in one of her bases, what is the probability that Bob will find the photon to be
vertically polarized if he uses the other basis?
The angle between bases is 45.

The probability is .

(b) Alice sends a key to Bob using the BB84 protocol. Name the principle that prevents an
eavesdropper (Eve) from intercepting Alices photon, and sending an exact copy on to
Bob, keeping a copy for herself.
This is the 'no-cloning theorem'. The linearity of operators in quantum mechanics forbids
the cloning of quantum states.
(c) Why will it do Eve no good to intercept Alices photon, measure its polarization in a
selected basis, and send a photon of this polarization to Bob?
Eve has no knowledge of the basis in which Alice prepared the photon, or the basis in
which it will be detected by Bob.
If Alice and Bob are using the same basis, and Eve uses a different one, then there is a
50% chance of her interception being betrayed when Alice and Bob compare notes.

QUESTION 10
In the Coulomb model of a hydrogen atom, how many degenerate quantum states have
energy ER/9, where ER is the Rydberg energy? Explain how you obtained your answer
from the restrictions that apply to the quantum numbers l, m and m s.

From the formula sheet,

En =

ER
n

We immediately see that quantum number n = 3 from the given energy.

For a given n, quantum number l can be 0, 1, 2, ... , (n 1).
For a given l, quantum number m can be 0, 1, 2, ... , l
For each m, we can have ms =
As n = 3, l can take the value 0, 1 or 2.
For l = 0, m = 0

1 value of m

For l = 1, m = 0, +1, -1

3 values of m

For l = 2, m = 0, +1, -1, +2, -2

5 values of m
9 values of m in total.

Now, each value of m can have 2 values of ms

Therefore, the degeneracy is 2 x 9 = 18 degenerate states.

QUESTION 10
(a) What is the energy (in eV) of the photon emitted when an electron makes a transition
from the first excited state to the ground state of a triply-ionized beryllium atom (Z = 4)?
(Ignore reduced mass effects in this case and take ER = 13.6 eV.)
This is a hydrogen-like system. It is triply ionized, so we have 1 electron. We have gone
from state n = 2 to state n = 1.

E SCALED
= Z 2 H ER
R

From the formula sheet:

But we are told to ignore reduced mass effects, so:

SCALED

ER

= Z E R = 4 E R = 16 E R

Hence, the photon's energy is:

SCALED

E PHOTON =

ER

SCALED

E
+ R 2
1

1
3
= E SCALED
+ 1 = E SCALED
R
4
4 R

3
16 E R = 12 E R = 12 13.6 eV = 163 eV
4

(b) What is the energy of the photon emitted when a muon bound to a beryllium nucleus
makes a similar transition to that described in part (a)? (You can take the mass of a muon
to be 207me, and the mass of a beryllium nucleus to be 16,560m e, where me is the mass of
an electron.)
Now, we have to take the reduced mass effects into account:
=

m muon m nucleus
207 me 16560 me
=
= 204 m e
m muon + m nucleus
207 me + 16560 me

The energy of the photon is thus:

4

E PHOTON = 204 163eV = 33252 eV = 3.33 10 eV

QUESTION 11
(a) In the LCAO approximation, which of the following three pairs of atomic orbitals,
centred on different atoms in a diatomic molecule, produce molecular orbitals?
(1s0 , 1s0), (2p0 , 2p0) and (2p1 , 2p1)
Looking at 1s0, the subscript '0' is the m quantum number value. Thus m = 0, and |m| = 0.
Therefore (1s0 , 1s0) combines to give a molecular orbital.
For 2p0, again we have m = 0 and |m| = 0. Thus, (2p0 , 2p0) also combines to give a
molecular orbital.
For 2p1, we have m = 1 and |m| = 1. Hence, (2p1 , 2p1) combines to give a molecular
orbital.
(b) The ground-state electronic configuration of the diatomic oxygen molecule O 2 is
12g 12u 22g 22u 32g 14u 12g
Given that 1g , 2g , 3g and 1u are bonding orbitals while 1u , 2u and 1g are
antibonding orbitals, what is the formal bond order of the O2 molecule?
Here, the superscript is the number of electrons.
Formal bond order =

no. of electrons in bonding orbitalsno. of electrons in antibonding orbitals

2
( 2 + 2 + 2 + 4 ) (2 + 2 + 2) 10 6
=
=
=2
2
2

(c) In one or two sentences, identify the feature of the ground-state electronic
configuration of the O2 molecule that allows it to be in a triplet state in the ground-state
configuration.
The 12g orbital is the highest orbital with 2 electrons, but this orbit is doubly degenerate
and can hold 4 electrons. So the possibilities are:
1
( )
2

1. The singlet antisymmetric state:

2. The triplet symmetric states:

or

or

1
( + )
2

QUESTION 12
(a) With the aid of a diagram, distinguish between the following types of radiative
transition: absorption, stimulated emission and spontaneous emission.
Reproduce figure 8.1 on page 196 of Book 3:

In absorption, the atom absorbs a photon, going up an energy level.

In stimulated emission, the atom absorbs a photon, dropping an energy level and emitting
a different photon.
In spontaneous emission, the atom emits a photon, dropping an energy level, without any
external stimulus.
(b) Which of these types of radiative transition has a probability that can be predicted
directly using time-dependent perturbation theory?
In absorption and stimulated emission, the interaction between an atom and external
radiation is through electron dipole approximation. If this is small enough we can use
perturbation theory.
Which of these types of radiative transition are subject to selection rules?
All 3 types of radiative transition are subject to the selection rules.

__________________________________________

(a)

TISE from Equation Booklet

Inside the well V(x) = 0 so

Therefore

)))

So
(b)

because we have odd x odd x odd = odd and integral is symmetric about

origin

because we have odd x even = odd and integral is symmetric about

origin
(c)

(
)

Substitute

( (

Units are right (L).

(d)
(

])

The double differentiation is evaluated in a) minus the -1/2m. The stuff inside the square brackets is
just a constant and can be taken outside the integral. It says in the question that 2 is normalised, so
the integral is just 1. Ive not used the first given definite integral, but this could be used to evaluate
the integral.
The units are right since we normally think k for momentum and k = 2/.

Beam of particles incident from left, each of mass m and energy E > 0, to a step potential:( )

Where U = 3E/4
General TISE solution is given as:( )

(a)
Use TISE to obtain expressions for k1 and k2. Show that k2 = k1/2.
TISE is as follows, from Equation Booklet:

( )

Substituting the given general solution into the TISE for the 2 regions:()
(
( (

)
)

)
)

)
)

The above can only be satisfied for all x if:-

( )
(

Applying similar for (i)

Substituting for U=3E/4

( )

(b)
The constant D is zero because physically there is no reflection in the region x > 0 i.e. no wave
travelling towards decreasing x in this region.
(c)
The boundary conditions at x=0 are that (x) is continuous and because V(x) is finite
continuous at x=0.
(d)
| |
We use the boundary conditions to calculate the ratio of B divided by A.
The continuity of at x=0 implies:( )
The exponents raised to power 0 are just 1.
The continuity of

at x=0 implies (again the exponents are 1 at x=0):-

( )

Eliminating C between (1) and (2), divide (2) by (1)

(

Dividing top and bottom of LHS by A and moving k1 to the RHS

(

Solving for B/A

(

( )

is also

Substitute answer from a)

Inserting this in formula for R:R = 1/9 QED

Theres no reminder of the value of R in the Equation Booklet, but I remember it from its definition
and then there are a few sanity checks:R+T=1
So R must be less than 1
j (the current) is speed (momentum / m) i.e. k/m multiplied by intensity of particle flow so you get:| |
Since the reflection is in the same region the ks (and other constants) cancel.

(a)

[ ]

is an eigenvector of with eigenvalue .

Thus

][ ]

A measurement of Sz in state |A>initial is certain to give a value of /2.

(b)

][ ]

][ ]

[ ]
[

[ ]

(c)

[ ]

So projecting |A>initial onto

are conjugate of kets.

][ ]

][ ]

i.e. using

and orthogonally of basis. Note bras

So

So at any
, this step isnt in the Equation Booklet so I had to remind myself. There is a hint in
( )
the Wave Mechanics section ( )
.

[ ]

[ ]

(
(

)
]
)

Using Equation Booklet (Mathematics section)

]
)

(
(

)
]
)

(d)
The probability (Pz+) that +/2 will be measured at

in the z direction in state |A>

This is effectively the overlap integral. We already know [ ] is the eigenvector of Sz that has an
eigenvalue of +/2 from (a). The equivalent row matrix is [

|[

][

(
(

)
]|
)

The probability (Pz-) that /2 will be measured at

)
in the z direction in state |A>

The row matrix equivalent of the down state in direction z is [

worry about conjugates.

|[

][

(
(

)
]|
)

].

]. Its real so we dont need to

Since it must be measured up or down the sum of the 2 probabilities should equal 1
(

(a)
Usual normalization of Spherical Harmonics

Where

In particular

( )

and
)

( )

( )

( )

][ ]

(b)
| |
| |
Using given definite integral
| |
Rearranging for A and choosing A real and positive

(c)
(

| |

Using given definite integral

| |
Unit are correct, but the answer is 5 times the Bohr radius. The Bohr radius is the average radius for
a hydrogen atom in it ground state (n=1). The given state is an excited state (n=2) so maybe it is OK.
Book 3 page 37 shows the Bohr orbit radius in various states is given by
, which for n=2 is 4a0.
So of the right order!

(d)
Radial Probability Density (RPD)
|

( )|

Calculate RPD for state

| | |

( ) given in question
| |

If we differentiate RPD with respect to r and set it equal to zero we can calculate when the RPD is at
its maximum. This might be what they mean by most likely.
| | [

Maximum is at
So most likely value for r is 4a0.

Chris Clarke's answer for SM358 2007 paper q18

21/9/12

This question concerns low-lying energy levels in a helium atom (Z = 2). In your answer,
you may denote the two single-particle helium atom orbitals of lowest energy by 1s and
2s . The combined spin state of the two electrons may be denoted by a spin ket of the
form |S, MS > , where S is the total spin quantum number and M S is the total magnetic
quantum number.
(a) Ignoring electronelectron repulsion, write down the total wave function corresponding
to the ground-state configuration of a helium atom. Specify the energy of this configuration
in terms of the Rydberg energy, E R .
At the ground state, we have S = MS = 0.
Thus, the total wave function is:

gs = 1s (r 1 ) 1s (r 2) 0, 0

The ground state energy is:

22 E R
22 E R
E gs = E 1s + E 1s = 2 2 = E R (4 4 ) = 8 E R
1
1
(b) Ignoring electronelectron repulsion, write down the four possible total wave functions
that correspond to the first excited-state configuration of a helium atom. In each case,
comment on whether the spatial and spin parts of the total wave functions are symmetric
or antisymmetric. Specify the energy of the first-excited configuration in terms of the
Rydberg energy, ER .

Wave function

Spatial part

Spin part

1
[ 1s (r 1) 2s ( r 2) + 2s (r 1) 1s ( r 2 )] 0,0
2

Symmetric

Antisymmetric singlet

1
[ 1s (r 1) 2s ( r 2) 2s (r 1) 1s ( r 2 )] 1, 1
2

Antisymmetric

Symmetric triplet

1
[ 1s (r 1) 2s (r 2) 2s (r 1) 1s ( r 2 )] 1, 0
2

Antisymmetric

Symmetric triplet

1
[ 1s (r 1) 2s ( r 2) 2s ( r 1) 1s ( r 2 ) ] 1,1
2

Antisymmetric

Symmetric triplet

The energy of the 1st excited state is:

E1

st

excited

= E 1s + E 2s =

22 E R
1

22 E R
2

4
4
= ER
= 5 E R
1
4

(c) Use first-order perturbation theory to obtain an expression for the ground-state energy
of a helium atom, taking the Coulomb repulsion e 2 /4 r 12 of the electrons into account.
Your answer should contain an explicit integral, but you should not attempt to evaluate
this integral.
Including the Coulomb repulsion, the Hamiltonian operator is:
H = h1 + h2 +

e2
4 0 r 1 2

In 1st order perturbation theory, we will choose h1 + h2 to be the unperturbed Hamiltonian,

and the perturbation will be the Coulomb repulsion. Therefore:
= H(0) + H

(0)
H = h1 + h2

where

and

H =

e2
4 0 r1 2

The total wave function describing the ground state of the unperturbed problem is:
gs = 1s (r 1 ) 1s (r 2) 0, 0
and the ground state of the unperturbed energy is:

E (0gs) = E 1s + E 2s = 2 E S

Hence, the 1st order correction to the ground state energy is:
(0 )
(0)

E(1)
gs = gs H gs

= 0, 0 0, 0

e2
(r 1 ) ( r 2 )
(r ) (r ) d V 1 d V 2
4 0 r 1 2 1s 1 1s 2

1s

1s

But the singlet spin ket is normalised, hence 0,0 0, 0 = 1 and:

E gs = 1s (r 1 ) 1s ( r 2)
(1)

e2
1s ( r 1) 1s (r 2) d V 1 d V 2
4 0 r 1 2

(d ) In the first excited configuration of a helium atom, are the triplet states higher or lower
in energy than the singlet state? In two or three sentences, use your answer to part (b) to
describe the physical reason for this energy-ordering.
Triplet states are lower in energy than singlet states. The singlet state has a symmetric
spatial wave function, so the electrons are likely to be close together, thus having a large
mutual potential energy. However, the triplet states have antisymmetric spatial wave
functions, so the electrons are likely to be further away from each other, and hence have a
lower mutual potential energy.