SM358 Exam 2013

Question 1 (a)
The energy eigenvalues of a cubic three-dimensional infinite square well of length L are given
by the following formula:
(

Therefore nx, ny and nz must have one of the following selections for Einit:

nx

ny

nz

3
1
3

1
3
1

1
1
1

Einit is triply degenerate.

Therefore nx, ny and nz must have the following selection for Efin:

nx

ny

nz

Efin is not degenerate.

Page 1 of 54

Question 1 (b)

Page 2 of 54

Question 2 (a)
As 2(x) and 3(x) are normalized, we can apply the coefficient rule:
|

| |

|
| |

| |

| |

Choosing N to be real and positive:

Question 2 (b)
The possible values of the energy in the given state are 2 and 3. The probabilities P2 and
P3 of these energies at time t = 0 are given by the coefficient rule:
| |
| |

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Question 2 (c)
The expectation value of the energy <E> is

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Question 3 (a)
(

))

Question 3 (b)
By the sandwich integral rule:

| |

)|

| (

)|

Therefore:

Because the energy eigenfunctions are orthonormal:

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Question 3 (c)
Kinetic energy Ekin and momentum are related thus:

)(

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Question 4 (a)
Borns Rule: For a single particle in one dimension, in a state described by the wave function
(x, t), the probability P of finding the particle at time t in a small interval x, centred on
position x, is
| (

)|

The given range is centred on x = a, with x = 0.02a. The probability P that, at time t = 0, the
particles position is in the given range is
| (

)| (

|(

| (

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Question 4 (b)
Borns Rule for Momentum: For a one-dimensional free-particle wave packet

( )

the probability P of finding the momentum to lie in a small interval

, centred on

, at

time t is
| ( )|

, so k = a1, and k = 0.02a1. The probability P that,

The given range is centred on

at time t = 0, the particles momentum is in the given range is

|(

| (

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Question 5 (a)
|

| |

( |

|) ( |

| )

Because the vectors are orthonormal

| |

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Question 5 (b)
|

|
|

( |

|)( |

|
(

| )

|
(

| |

|
)

|
)

| |

|
| ( )
|
because is an Hermitian operator and one property of any Hermitian operator is
|

Therefore
| |

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Question 5 (c)

| |

| |

Therefore

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Question 6 (a)

( )
(

)(

( )
Therefore f () is an eigenfunction of , with eigenvalue

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Question 6 (b)
The Generalized Uncertainty Principle states:
|[ ]|
| |
| |

| |

| |

We found in part (a) that for a state with the -dependence of f (), Lz has the definite value
. Therefore the expectation value <Lz> must have the value
|

Therefore

If an observable A has a definite value, it follows that the uncertainty A = 0. If, therefore, Lx
or Ly has a definite value, then the above inequality becomes

which is impossible. Therefore neither Lx nor Ly can have a definite value in this state.

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Question 7 (a)
The spin state | is entangled. An entangled two-particle spin state cannot be expressed as a
product of two one-particle spin states, one of which describes the spin of particle-1 and the
other of which describes the spin of particle-2. Given a spin state
|

| can only be expressed as a product of two spin states if

For the spin state |

. It follows that | is an entangled state.

Question 7 (b)
If state | is measured and the two particles are found to have opposite z-components of spin,
then the measurement must have collapsed the state onto either the second or third term of the
initial state. As the initial state is normalized, we can use the coefficient rule to determine the
probabilities of each of these two mutually exclusive outcomes:
(| )

(| )

| |

| |

As these are mutually exclusive outcomes, the probability of measuring either of them is the
sum of the individual probabilities:
(|

| )

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Question 7 (c)
As

is the eigenvalue of | , if the initial state is measured and both particles are found
, it follows that the measurement has caused the initial state to collapse to

to have

. By the overlap rule, the probability P of this happening is:

the state |

| |

The probability amplitude is therefore

( )(

|( |

)(

( )(

)(

( )(

)(

( )(

)(

The probability P is therefore

|

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Question 8
(a) False.
(b) True.
(c) True.
(d) True.
(e) False.

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Question 9 (a)
The most probable value for r is found by optimizing the radial probability density:

( )

( )

For a maximum, let this equal zero:

(

The most probable electron-proton separation is a0.

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Question 9 (b)
The expectation value of the electron-proton separation is

( )

)( )(

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Question 10 (a)
For a hydrogen-like atom

For He+ in its ground state, n = 1 and

Therefore
(

)( )(

)(

Question 10 (b)
In the independent model, the ground-state energy Egs of the He atom is

)(

Question 10 (c)
The first-order perturbation correction Egs(1) to the ground-state energy of the He atom is
( )

( )

( )

( )

( )

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Question 11 (a)
As the two valence electrons have different values of l, they are non-eqiuvalent. Therefore:
|

The possible values of L are L = 1, L = 2 and L = 3. The possible values of S are S = 0 and
S = 1.

Question 11 (b)
In the absence of spin-orbit interactions an atomic term (L, S) has degeneracy
(

)(

Therefore the atomic term with L = 1 and S = 1 has degeneracy

(

)(

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Question 11 (c)
Assuming the LS-coupling scheme applies, an atomic term (L = 1, S = 1) splits into atomic
levels with total angular momentum quantum number J:
|

The possible values of J are J = 0, J = 1 and J = 2.

The degeneracy of an atomic level is (2J + 1). Therefore the three atomic levels have the
following degeneracies:
J degeneracy
0
1
1
3
2
5

Page 21 of 54

Question 12 (a)
The formal bond order FBO of a molecule is defined as

where nb is the number of electrons in bonding orbitals and na is the number of electrons in
antibonding orbitals. In this case

Question 12 (b)
The Born-Oppenheimer Approximation allows us to calculate the electron energy
eigenfunctions for the H2+ molecule ion for a fixed proton separation R. These eigenfunctions
depend parametrically on R. For a given value of R, the effective potential energy function in
which the protons move is the sum of the electronic energy and the Coulomb potential energy
due to proton-proton repulsion. This sum is the total static energy of the molecule ion. If the
total static energy is plotted against proton-proton separation R for the ground state, the result
is the energy curve. This curve will have a minimum corresponding to the equilibrium
separation of the protons.

Page 22 of 54

Question 13 (a)
The general time-independent Schrdinger equation is

( )

( )

The time-independent Schrdinger equation for a one-dimensional infinite square well in the
region

is
( )

( )

Substituting 1 (x) for n (x) and letting n = 1, we get:

( )

( )

))

))

))

))

))

))

))

))

Therefore the time-independent Schrdinger equation is satisfied by 1 (x) provided its energy
eigenvalue E1 is

Page 23 of 54

Question 13 (a) continued

Substituting 2 (x) for n (x) and letting n = 2, we get:
( )

( )

))

))

))

))

))

))

))

))

Therefore the time-independent Schrdinger equation is satisfied by 2 (x) provided its energy
eigenvalue E2 is

Page 24 of 54

Question 13 (b)
The boundary condition that must be satisfied is that the energy eigenfunctions n (x) must be
continuous at

and at

. As (x) = 0 everywhere outside the well, this

means that
(

and

( )

( )

Therefore both 1 (x) and 2 (x) satisfy the boundary conditions.

Page 25 of 54

Question 13 (c)
The expectation value of position x in the state described by 2 (x) is calculated using the
sandwich integral rule:

( )

( )

(Time-dependent phase factors need not be included as they combine to give 1.) Because the
eigenfunction is equal to zero outside the well, we need only integrate across the well:

The integrand is an odd function of x, being the product of one odd function (x) and one even
function (sin2). It follows that when we integrate across an interval centred on the origin the
result will be zero. Therefore

Page 26 of 54

Question 13 (c) continued

The expectation value of x2 can be calculated using a similar sandwich integral:

( )

( )

Applying the same criteria as before, we get

To evaluate this integral we use the substitution

This gives us:

( )(

(
(

)(

)
)

Page 27 of 54

Question 13 (d)
The probability P that the particle is found in the given range can be calculated using Borns
Rule:

( )|

Using the same substitution as before, we get

( )(

( )( )

Page 28 of 54

Question 14 (a)
In the region x 0,

Combining these relations, we get

Page 29 of 54

Question 14 (a) continued

In the region x > 0, let k2 be the angular wave number. Then the relations corresponding to the
four above are:

Combining these relations, we get

The general solution to the time-independent Schrdinger equation in this region can be
expressed as
( )

where

Therefore = k.

Page 30 of 54

Question 14 (b)
C = 0. Cex represents a beam travelling in the negative x-direction in the region x > 0, but
there is no boundary in this region to reflect the transmitted beam, so there can be no such
reflected beam in this region.

Question 14 (c)
The boundary conditions that (x) must satisfy at x = 0 are:
(1) (x) must be continuous at x = 0.
(2)

( ) must be continuous at x = 0.

These lead to the following two equations:

[ ]

Using the result from part (a), k = , the second equation can be simplified:
(

Multiplying this equation by i gives us

[ ]
Adding [1] and [2] gives us
(

Page 31 of 54

Question 14 (d)
| (x) |2 is the probability density (in one dimension, a probability per unit length). In this
context it represents the linear number density of particles in the beam (i.e. number of
particles per unit length, with the dimensions m1).
Using the results of part (c), in the region x 0
( )
| ( )|

( ) ( )

)(
| |

| |

| |

| |

| |

| |

| |
| |
| | (

| |

| |

(
(

)
))

Question 14 (e)

Page 32 of 54

Question 15 (a)
All the particles emerging from P1 will have

. The fraction of these that emerge

( ) rule; and the fraction of these that emerge from P3, P4 and

from P2 is given by the

P5, and that are detected in the upper component of the spin analyzer can similarly be
calculated. So the fraction F of the particles emerging from P1 that are detected by the upper
component of the analyzer (i.e. that have
(

) are:

)(

)(

)(

)(

Question 15 (b)
|

The normalization condition is

|
[

] [ ]
| | (

)
| |

choosing N to be real and positive.

Page 33 of 54

Question 15 (c)
au is the coefficient of | in the direction of | . Therefore

]
(

[ ]

ad is the coefficient of | in the direction of | . Therefore

[ ]
)

By the coefficient rule, the probability P+ of measuring | and finding

|

Similarly, the probability P of measuring | and finding

|

is

is

Page 34 of 54

Question 15 (c) continued

The expectation value of Sy is given by the sandwich rule:
| |

] [

[ ]

][ ]
(

Page 35 of 54

Question 15 (d)

[
[

[ ]

[ ]

|
is

Therefore the eigenvalue corresponding to |

|

.
]

[ ]

|
Therefore the eigenvalue corresponding to |

is

Page 36 of 54

Question 15 (d) continued

(

[ ]

[ ])

]
]

Page 37 of 54

Question 16 (a)
A fermion is a particle whose spin quantum number s is a half integer:

A boson is a particle whose spin quantum number s is an integer:

A composite particle is a fermion if it contains an odd number of fermions; otherwise it is a

boson. A neutral atom of

is comprised of 37 electrons, 37 protons and 50 neutrons. Each

of these particles is a fermion, so the atom contains 124 fermions. A neutral atom of

is

therefore a boson.

Page 38 of 54

Question 16 (b)
Under particle exchange
(

Therefore A (x1, x2) is a symmetric spatial wave function.

Under particle exchange
(

Therefore B (x1, x2) is an antisymmetric spatial wave function.

The total wave function of a system of two particles is the product of the systems spatial
wave function and its total spin state.
A system comprising identical bosons must be described by a symmetric total wave function.
A system comprising identical fermions must be described by an antisymmetric total wave
function.
A symmetric total wave function is the product of either a symmetric spatial function and a
symmetric spin state, or an antisymmetric spatial function and an antisymmetric spin state.
An antisymmetric total wave function is the product of either a symmetric spatial function and
an antisymmetric spin state or an antisymmetric spatial function and a symmetric spin state.

(1) Identical bosons => symmetric total wave function. Symmetric spin state => symmetric
wave function => A (x1, x2) is possible.
(2) Identical bosons => symmetric total wave function. Antisymmetric spin state =>
antisymmetric wave function => B (x1, x2) is possible.
(3) Identical fermions => antisymmetric total wave function. Symmetric spin state =>
antisymmetric wave function => B (x1, x2) is possible.
(4) Identical fermions => antisymmetric total wave function. Antisymmetric spin state =>
symmetric wave function => A (x1, x2) is possible.

Page 39 of 54

Question 16 (c)
A pair of electrons comprises a system of identical fermions, so it must be described by an
antisymmetric total wave function. Therefore the antisymmetric spatial state B (x1, x2) must
be accompanied by one of the symmetric spin states (i.e. one of the triplet states):

(|

| )

Similarly, the symmetric spatial state A (x1, x2) must be accompanied by the antisymmetric
spin state (i.e. the singlet state):

(|

| )

Page 40 of 54

Question 16 (d)
The expectation value of x1x2 for the spatial state A (x1, x2) can be calculated using the
sandwich integral rule:

)]

The first of these double integrals can be expressed as the product of two single integrals:

The first of these single integrals has an odd integrand integrated from to +, so the entire
doule integral evaluates to zero.
The same argument applies to the third double integral above, which is identical to the first
but with the subscripts 1 and 2 exchanged. Therefore it too vanishes. This leaves just the
middle double integral, which can be expressed as a product of two single integrals:

For the symmetric spatial state

)(

)(

Page 41 of 54

Question 16 (d) continued

The expectation value of x1x2 for the antisymmetric spatial state B (x1, x2) can be calculated
using the sandwich integral rule. The working is the same as for the symmetric state except
that the middle double integral will have a 2 in front of it instead of a +2. Therefore, for the
antisymmetric spatial state

Question 16 (e)
(

The expectation value of a composite function that is a sum or difference of simple functions
is equal to the sum or difference of the expectation values of the simple functions. So
(

For the symmetric spatial state, A (x1, x2)

(

For the antisymmetric spatial state, B (x1, x2)

(

Page 42 of 54

Question 17 (a)
The normalization condition for spherical harmonics is:

Then:

| |

| |

| | (

)( )
| |

choosing A to be real and positive.

Page 43 of 54

Question 17 (b)
(

So the orbital angular momentum quantum number l = 1, and the magnetic quantum number
m = 1.
(

Page 44 of 54

Question 17 (b) continued

If

) is an eigenfunction of with eigenvalue

, then:

))

Using the anticipated eigenvalue:

)
(

Therefore

) is an eigenfunction of with eigenvalue

.
Page 45 of 54

Question 17 (c)
If | is an eigenfunction of

, with eigenvalue
(

)|

, then

Noting that the orbital angular momentum operator acts on only the angular part of the energy
eigenfunction and the spin operator acts on only the spin ket, we get:
(

)|

)|

)|

)| )

)|

)|

)|

)|

)| )

)|

)|

|
Therefore | is an eigenfunction of with eigenvalue
Check:

|
|
Therefore mj = 1/2.

Page 46 of 54

Question 17 (d)
For a given value of n, l can take the following values:
(

For each of these values of l, m can take the following values:

(

)(

The selection rules for radiative transitions are:

For photon emission, n must decrease:

For n2 = 3, the only allowed values for l are 0, 1, 2:

For l2 = 2, the only allowed values for m are 2, 1, 0, +1, +2:

For n2 = 2 and for n2 = 1, there are no allowed values for l, so these transitions are forbidden.
So the only allowed initial transition is from (4, 3, 3) to (3, 2, 2).

Page 47 of 54

Question 17 (d) continued

For n3 = 2, the only allowed values for l are 0, 1:

For l3 = 1, the only allowed values for m are1, 0, +1:

For n3 = 1, there are no allowed values for l, so this transition is forbidden.

So the only allowed second transition is from (3, 2, 2) to (2, 1, 1).

For n4 = 1, the only allowed value for l is 0:

For l4 = 0, the only allowed value for m is 0:

So the only allowed third transition is from (2, 1, 1) to (1, 0, 0), which is the ground state.

Page 48 of 54

Question 17 (d) continued

initial state

ground state

n
4
3
2
1

l
3
2
1
0

m
3
2
1
0

The energy of a photon emitted during a transition in this model is

The most energetic photon will be emitted during the final transition from (2, 1, 1) to (1, 0, 0):
(

Page 49 of 54

Question 18 (a)
( )

( )

| |

( )

( )

( )

| |

( )

( )
( )

( )

( )

Then the estimated energy of the ground state (n = 0) is:

( )|

Now:

Therefore:

Page 50 of 54

Question 18 (a) continued

Applying the same procedure to the first excited state (n = 1), the estimated energy is:

( )|

Now:

Therefore:

The energy emitted by a photon when the oscillator makes a radiative transition from the first
excited state to the ground state is approximately:

Page 51 of 54

Question 18 (b)
||

||

|) (|

||

||

| |

|
|

|)(|

Therefore:
||
|

Page 52 of 54

Question 18 (c)
||
|

To solve this we differentiate the funtion with respect to , set the resulting derivative to zero,
solve for , check that our value is a minimum, then substitute this value of into the
inequality to get our estimate of the ground-state energy. (As is just a constant multiple it is
convenient to ignore it during the differentiation and reinsert it at the end.) Using the quotient
rule for differentiation:
(

)(

)(

For a minimum, set this to zero, which means the numerator must be zero:

The minimum value of is then

Page 53 of 54

Question 18 (c)
Putting this into our estimate of the ground-state energy gives us:

Our estimate of the ground-state energy is

We can be certain that the exact value of the ground-state energy is less than or equal to this
value.

THE END

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