Solutions
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Equations for Light

Heisenberg Uncertainty Principle

E = h
c =

2
[A, B]ave
AB
2
pq

DeBroglie Relation
h = p

Radial Distribution Function

Operators
H =
H(harmonic oscillator) =
H(rotation) =
I =
H(hydrogenic) =
[A, B] =
Aave =
=

p2
+V
2m
p2
1
+ kx2
2m 2
J2
2I
mr2
p2
Z e2

2m 4o r
AB B A


Ad


d
m1 m2
m1 + m2

P (r) = r2 R R

Eigenvalues and Eigenfunctions

2 2

n h
particle in a box: En = 8mL
n = 1, 2, 3, 4, . . .
2,
1
harmonic oscillator: En = (n
+ 2 )ho ,
n = 0, 1, 2, 3, . . .
1
k
o = 2 m

j = 0, 1, 2, 3, . . .
h2

rigid rotor: Ej = j(j + 1) 2I ,

m = j, . . . , j
2
2
J Yj, m = j(j + 1)
h Yj, m
Jz Yj, m = m
hYj, m

n = 1, 2, 3, . . .
Z2
h2
1-electron atom: En = n2 2 me a2 , j = 0, . . . , n 1
o

m = j, . . . , j

n(x) = L2 sin(nx/L)
2
n(x) = Nn Hn (y)ey /2
Yj, m (, ) = j, m ()ei m

n j m (r, , ) = Rn j (r)Yj, m (, )

n j m s ms =

n j m

or

n j m
Z r
Rn j (r) = r (polynomial in r of order [n-j-1])e n ao
j

P.T.O. . . .

Fundamental constants and conversion factors

h
c
R
me
ao
1J

=
=
=
=
=
=

6.626 1034 Js
3 108 ms1
8.31JK 1 mol1
9.11 1031 kg
0.529 1010 m
1 kg m2/s2

Complex numbers
eikx = cos(kx) + i sin(kx)
Spherical Polar Coordinates
dV = r2 dr sin d d
Integrals



sin(nx/L)dx = (L/n) cos(nx/L)

sin2 (nx/L)dx = 0.5x (L/4n) sin(2nx/L)

0

rn ea r dr =

n!
an+1

1. [5 marks] |(x)|2 is equal to the probability of nding the particle at

position x:
(a) Always
(b) Only if is positive.
(c) Only if is normalized.
(d) Only if is real.
Answer (c)

2. [10 marks] Write down the Hamiltonian for Lithium Hydride, LiH
Answer:
H = Te + Vnn + Vne + Vee
h
2 2
h
2 2
h
2 2
h
2 2
=
1
2
3

2 me
2 me
2 me
2 me 4
3e2
+
4
o RLi H
3e2
3e2
3e2
3e2

4
or1 Li 4
o r2 Li 4
o r3 Li 4
o r4 Li
e2
e2
e2
e2

4
or1 H 4
o r2 H 4
o r3 H
4
or4 H
e2
e2
e2
e2
e2
e2
+
+
+
+
+
+
4
o r1 2 4
o r1 3 4
or1 4 4
or2 3 4
or2 4 4
or3 4

3. (a) [15 marks] Decide whether or not each of the following wavefunctions obeys the Pauli Exclusion Principle for electrons:
i. (1, 2) = px (1) px (2)(1) (2)
Answer N

ii. (1, 2) = px (1) py (2)(1) (2)

Answer N

iii. (1, 2) = px (1) px (2)(1) (2)

Answer N

iv. (1, 2) = {px (1) py (2) + py (1) px (2)} (1) (2)

Answer N

v. (1, 2) = {px (1) py (2) py (1) px (2)} (1) (2)

Answer Y

vi. (1, 2) = px (1) px (2) {(1) (2) + (1)(2)}

Answer N

vii. (1, 2) = px (1) px (2) {(1) (2) (1)(2)}

Answer Y

viii. (1, 2) = {px (1) py (2) + py (1) px (2)} {(1) (2) + (1)(2)}
Answer N
3

ix. (1, 2) = {px (1) py (2) + py (1) px (2)} {(1) (2) (1)(2)}
Answer Y

(b) [15 marks] Starting from the orbital-product wavefunction for Lithium,
(1, 2, 3) = 1s(1)(1) 1s(2)(2) 2s(3)(3)
construct a wavefunction which obeys the Pauli exclusion principle.
Answer
(1, 2, 3) =
=
=
+
+

Det (1s 1s 2s)

(show working) . . .
1s(1) 1s(2) 2s(3)
1s(2) 1s(3) 2s(1)
1s(3) 1s(1) 2s(2)
1s(1) 1s(3) 2s(2)
1s(3) 1s(2) 2s(1)
1s(2) 1s(1) 2s(3)

4. (a) [5 marks] Plot the antibonding molecular orbital for H2+ along the
internuclear axis without worrying about normalization.
Answer

(b) [5 marks] Plot the probability density, again neglecting normalization.

Answer

(c) [15 marks] The wavefunction for the ground state of H2+ may be
approximated as a linear combination of atomic orbitals 1s A and
1sB ,
= 1sA + 1sB
i. Express the electron density for H2+ in terms of the atomic
orbitals, without worrying about normalization.
Answer
(r) = (r)(r)
= (1sA (r) + 1sB (r)) (1sA (r) + 1sB (r))
= 1sA (r)1sA (r) + 1sB (r)1sB (r) +
1sA (r)1sB (r) + 1sB (r)1sA (r)+

ii. Express the electron density as a sum of the atomic densities

and an additional molecular density, again without worrying
about normalization.
Answer
(r) = 1sA (r)1sA (r) + 1sB (r)1sB (r) +
1sA (r)1sB (r) + 1sB (r)1sA (r) +
= (atom A) + (atom B) +
1sA (r)1sB (r) + 1sB (r)1sA (r) +

(d) [25 marks] Consider the two-electron molecule H3+, and assume
that the three nuclei form an equilateral triangle. Starting from
the Hartree-Fock wavefunction for H3+ ,
(1, 2) = (1)(2){(1)(2) (1)(2)}
Expand the molecular orbital as a L.C.A.O. of atomic orbitals
1sA , 1sB and 1sC ,
= 1sA + 1sB + 1sC
By expressing in terms of the atomic orbitals show that the
Hartree-Fock wavefunction gives unphysical behaviour at long bondlengths.
Answer
(1, 2) = (1)(2){(1)(2) (1)(2)}
= (1sA (1) + 1sB (1) + 1sC (1)) (1sA (2) + 1sB (2) + 1sC (2)) {(1)(2) (1)(2)}
= 1sA (1) 1sA (2){(1)(2) (1)(2)}
+1sB (1) 1sB (2){(1)(2) (1)(2)}
+1sC (1) 1sC (2){(1)(2) (1)(2)}
+1sA (1) 1sB (2){(1)(2) (1)(2)}
+1sB (1) 1sA (2){(1)(2) (1)(2)}
+1sA (1) 1sC (2){(1)(2) (1)(2)}
+1sC (1) 1sA (2){(1)(2) (1)(2)}
+1sB (1) 1sC (2){(1)(2) (1)(2)}
+1sC (1) 1sB (2){(1)(2) (1)(2)}
There are nine terms in the expansion of the wavefunction. The rst
three terms, A(1)A(2), B(1)B(2) and C(1)C(2), have both electrons
on the same atom, ie they describe the ionic congurations HA HB+ HC+
etc. At long bond-lengths H3+ would be expected to dissociate to
HA HB HC+ etc, so the rst three ionic congurations are unphysical
at long bond-lengths. The remaining six terms, A(1)B(2) etc describe
the conguration HA HB HC+ etc and hence are physically reasonable at
long bondlengths.
7

5. The electrons in a cyclic polyene can be modelled as particles on

a ring. It is easiest to use polar coordinates r and . The Hamiltonian for a particle of mass m moving around a ring of radius r is
h
2 d2
H=
. The mass of an electron is 9.11 1031 kg, and the
2m r2 d 2
radius of the ring is 109 m.
(a) [75 marks] The following problems are for a single electron on
a single ring:
i. Draw a diagram showing the ring, a single electron, r and .

ii. Using the Hamiltonian above, explicitly calculate the eigenvalues and eigenvectors for a single electron on a ring. Do not
use any formulae from the data sheet.
Answer
The radius r is xed, so the eigenfunctions are functions of
, (). The eigenfunctions of d2 /d2 are ei, where is an
unkown constant,

h
2 d2 i
h
2 2 i
e
=
e
2m r2 d 2
2m r2
2

The eigenvalue of the eigenfunction e i is 2m

.
r2
(An equally good alternative set of eigenfunctions is cos
and sin .)
What values can take? The wavefunction must be singlevalued, ie when we go once around the ring the wavefunction

must return to its initial value,

(0) = (2 )
and hence
2 = 2n

where n = 0, 1, 2, . . .

ie
= 0, 1, 2, 3 . . .
(note that = 1 gives a dierent eigenfunction from = 1).
In conclusion, the eigenfunctions and eigenvalues of H are,
where n = 0, 1, 2, . . .
n() = ein
2 2
h
n
En =
2m r2

iii. What are the allowed values for the quantum number(s)?
Answer
n = 0, 1, 2, . . .

iv. What are the wavelengths of the eigenfunctions corresponding

to the lowest three eigenvalues?
Answer
When answering this question it helps to draw a circle or
radius r. Then cut the circle and straighten it out into a line
of length 2r. Then draw the wavefunction vs circle length.
E0 =
E1 = 2r
E2 = r

10

v. The total wavefunction, including spin, can be written as the

product of the spatial wavefunction and a spin wavefunction,
(, ) = ()
where the spin-function is either = or = . What are
the degeneracies of the lowest three eigenvalues? What would
the degeneracies be if the electron did not have spin?
Answer
The ground state E0 is doubly degenerate; the two degenerate
states are 0 and 0. The rst excited state is four-fold
degenerate; the four degenerate states are 1, 1 , 1
and 1 .
If the particle had no spin then all the degeneracies would be
halved. The ground state would be non-degenerate and the
rst excited state would be doubly degenerate.

vi. Draw an energy-level diagram showing the lowest ve energy

levels, their quantum numbers and degeneracies.

11

(b) [20 marks] Consider a system containing two non-interacting

copies of the above system, ie two widely separated rings each of
radius 109 m and each possessing a single electron. What are the
eigenvalues and degeneracies of the lowest three eigenvalues?
Answer
Because the two systems are non-interacting, the Hamiltonian is
separable. So the energy of the combined system is the sum of the
energies of the individual rings.
The ground state energy is E0 0 = 0. The ground-state eigenfunction is four-fold degenerate; the four degenerate states are
0A 0B , 0A 0B , 0A 0B and 0A 0B , where A and B denotes ring A and ring B.
The rst excited state energy is E0 1 = E1 0 = E0 1 = E1 0 =
h2

. . The rst-excited-state eigenfunction is sixteen-fold de2m r 2

generate; the sixteen degenerate states are 0A 1B , 0A 1B ,
0A 1B , 0A 1B , and so on for 1 0, 0 1 and 1 0.
The second excited state energy is E1 1 = E1 1 = E1 1 =
2
E1 1 = 2 2mh r2 . This state is also sixteen-fold degenerate.

12

(c) [30 marks] Consider four electrons on a single ring. For

simplicity, treat the four electrons as independent particles, ie
ignore Coulomb interactions between the electrons.
i. Redraw the energy-level diagram for the lowest ve energy
levels of a single electron, and indicate which levels are occupied in the ground state by using up-arrows for electrons with
spin and down-arrows for electrons with spin.

ii. What is the total energy of the ground state?

Answer

13

E0(1) 0(2) 1(3) 1(4) = 2 2mh r2 .

iii. Is the ground state a singlet or a triplet?

Answer
Triplet (Hunds rules: not on the syllabus in Spring 2002).

iv. Calculate the absorption frequency for a transition from the

ground state to the rst excited state.
Answer
The lowest-energy transition is marked on the diagram,

14

h
2
E = E1 E0 =
0
2m r2
To convert this to a wavelength use
E = h = h c/

15

(d) [30 marks] Consider a single spinless particle on a single

ring. Using the normalized wavefunction,
() =

1
( 2)
18

calculate the average value for the energy. Is this above or below
the true ground-state energy?
Answer




=
=
=
=
=
=
=
=
=

<H > =

 2
0

since is normalised

 2
2

h2
d

2 m r2 0
d 2

h2  2 1

2 m r2 0
18
2  2
1 2

h
1
( 2)
2
2 m r 0 18
18

h2 1 3
[ /3 2]20
2
2
2 m r 18


h2 1  3
3
8

/3

4
2 m r2 182

h2 1 4 3
2 m r2 182 3
h
2 1 4 3
2 m r2 182 3

According to the variational theorem, this energy is above the true

ground-state energy. This is easy to verify in the present case since
the true ground-state energy is zero.

16

(e) [40 marks] Consider a single spinless particle on a single

ring in the first excited state.
i. What is the degeneracy of this state? For each of the degenerate states, calculate the average value of the angularmomentum operator,
h
d
J =
i d
Answer
The degeneracy of this state is two; the two states are e i and
ei . The average value of J for the rst state is,
< J > =

2 i h d i
e
e
0
i d

2

2 i h d i
e
0 e
i d

2

=
=

ei ei

i ei
0 e

2 i h i
ie
0 e
i

2
i
ei
0 e

2

0 h

2
0 1

= h

So the average value of J for the rst state is h

. Proceeding
similar for the second state, one nds that the average value
of J is
h.

17

ii. Consider a complex linear combination of the degenerate

states, eg,
= state1 + i state2
Evaluate the average value of the angular momentum operator
for , and also for .
hint: To shorten the computation, use the fact that state1
and state2 are orthogonal.
< J > =
=
=
=

2

(1 + i2) J (1 + i2)

0 (1 + i2 ) (1 + i2 )

2
J 1 + (i2) J i2 + J i2 + (i2) J 1
0

2

2

0 1 1 + (i2 ) i2 + 0 + 0

2
h
h
+ ieiJ ei iei J ei
0

2

0 1 1 + (i2 ) i2 + 1 i2 + (i2 ) 1

2
h
+ (i)i(
h) + i J 2 i J 1

2

2

1 + 1 + +0 + 0
d i
iei hi d
e

d i
+iei hi d
e

+iei hi (i)ei

iei hi iei

4
h
iei2h

0 ie
=
4
i2
i2
i
h[ ei2 + ei2 ]20
=
4
but eix has period 2 so each expontential in the numerator gives zero
= 0

2

i2

18

Spare page

20

OLD EXAM Solutions

1. (6 pts) In an X-ray photoelectron experiment, a photon of
wavelength 150 pm ejects an electron from the inner shell of an atom
and it emerges with a speed of 2.14x107 m/s. Calculate the binding
energy (= work function) for this electron (in eV).
i) Calculate the kinetic energy of the electron ( = 1/2 m v^2 )
ii) Calculate the energy of the photon ( E = h nu)
iii)Binding energy = Photon Energy - Kinetic Energy
Laser Excitation
Kinetic Energy
Ionization Threshhold

Bound Electron

2. (6 pts) Is the function (x) = cos(kx) + sin(kx) an eigenfunction

of the operator = d2/dx2? If the answer is "YES", what is the
eigenvalue? (Show work)
i) d^2/d x^2 psi = - k^2 cos(kx) - k^2 sin(kx)
The wavefunction is an eigenfunction of the second derivative operator, with eigenvalue k^2

3. (6 pts) Given () = Nexp(-im) with 0 2, m = integer, find

the factor N that normalizes ().
N = 1/sqrt(2 pi)

4. (10 pts) The energy (E) of the classical one-dimensional

harmonic oscillator is given by the expression
E = px2/2m + 0.5kx2
where k = force constant; m = mass; and px = momentum.
(a) (5 pts) What is "x" in the above expression? [A one sentence
definition will do.]
x is the position of the particle; in classical mechanics x(t) is the
trajectory.

(b)(5 pts) Write the expression for the quantum mechanical

harmonic oscillator Hamiltonian
H = -hbar^2/2m d^2/dx^2 + 0.5 k x^2

5. (6 pts) The energy separation between the vibrational levels in a

14N2 molecule is found to be 4.8x10-20 J. What is the zero-point
vibrational energy for a 14N2 molecule (in J)?
E_n = h nu( n + 1/2)
spacing = E_n - E_n-1 = h nu
zero point = 1/2 h nu
So zero point energy = 1/2 spacing

6. (12 pts total) Let 1 and 2 be two normalized eigenfunctions of a

hermitian operator with eigenvalues 1 and 2, respectively. Assume
1 and 2 are different (1 2)
a. (6 pts) Evaluate the integral 2* 2 d
Give each step of the evaluation clearly. You will not receive any
credit, if you only show (guess) the answer.
int psi^* O psi

int psi^* E psi

= E int psi^* psi
= E

So the inegral equals the eigenvalue.

b. (6 pts) Evaluate the integral 1* 2 d

Give each step of the evaluation clearly. You will not receive any
credit, if you only show (guess) the answer.
int psi_1^* O psi_2 = int psi_1^* E_2 psi_2
= E_2 int psi_1^* psi_2
= 0 since the eigenfunctions of a hermitean operator are orthogonal

7. (6 pts) The magnitude of the total angular momentum is measured for

a particle with the result |L| = 6h
If Lz is now measured for this particle, what is (are) the
possible value(s) obtainable?
|L|^2 = 6 hbar^2

= l(l+1) hbar^2

So the angular momentum quantum number l = 2

The z component is m hbar, where m is between -2 and 2.
So the values obtainable are -2hbar, -hbar, 0, hbar, 2hbar.
8. (30 pts total) A particle of mass m in a one-dimensional box of
length L is in the state characterized by n = 3.
a. (8 pts) Draw a sketch of the wavefunction and a sketch of the
the probability density for this particle (label the axes!).
Wavefunction

Density

2/3L

1/3L

b. (4 pts) What is(are) the most likely location(s) of this particle?

The most likely locations occur where the density is at a maximum,
ie at L/6, L/2, 5L/6

c. (6 pts) What is the probability of finding this particle in the

central third of the box?
The integral of the density from 0 to L must equal one.
Looking at the density, it is clear by symmetry that the integral over the middle third of the box is
one third of the total, ie one third of one, ie 1/3.
Answer: Probability = 1/3.

d. (6 pts) For this particle, what is <H>?

<H> = E_3 = hbar^2 n^2 3^2/2 m L^2

e. (6 pts) For this particle, what is <px>?

<p_x> = 0
The easiest way to see this is
<p_x> = int psi^* p_x psi
= int even odd even
= int odd
= 0 by symmetry

since odd times even = odd

Alternatively, you can actually evaluate the integral.

9. (12 pts) A particle of mass m and moment of inertia I rotates freely

in three dimensions in a state described by the spherical harmonic

Y3,-2(,)
(a) (6 pts) Find the total rotational energy of this particle
H = L^2/2 I
Y is an eigenfunction of L^2 with eigenvalue hbar^2 3(3+1)
So Y is also an eigenfunction of H, with eigenvalue hbar^2 3(3+1)/2 I
So the energy is hbar^2 3(3+1)/2 I

(b) (6 pts) In a single measurement of the z-component of the angular

momentum for this particle, what is the probability of obtaining the
value 1h ?
The possible values are

3hbar, 2hbar, 1hbar, 0, -1hbar, -2hbar, -3hbar.

All 7 energy levels are degenerate and hence equally probable.

So the probability of getting 1hbar is 1/7.

10. (6 pts) What are the values of s and ms for an electron in the
spin state ?
s = 1/2,

m_s = -1/2

Operators
H = (-h2/2m) 2 + V
2 = 2/x2 + 2/y2 + 2/z2 = 2/r2 + (2/r)/r + (1/r2)2 =
2/r2 + (2/r)/r - (1/r2)(L2/h2)
2 = (1/sin2 )2/ 2 + (1/sin )/sin/
H = (-h2/2I)2/ 2
H = (-h2/2m)d2/dx2
Energies
En = n2h2/8mL2

n = 1,2,3,4

Wavefunctions
n(x) = (2/L)1/2sin(nx/L)

El = l(l+1)(h2/2I)

l = 0,1,2,3..

Yl,ml(,) = l,ml()ml()

Ev = (v + 0.5)h

v = 0,1,2,3..

v(x) = NvHv(y)exp(-y2/2)

E = J2/2I
E = h
E = 0.5mv2 = p2/2m
Miscellaneous
H = E

< > = d

i jd = ij

L2Yl,ml(,) = l(l+1)h2Yl,ml(,)

l = 0,1,2,3,4..

LzYl,ml(,) = mlhYl,ml(,)

ml = 0,1,2..l

pq h/2

= h/p

= c

[1, 2] = 12 - 21

= mAmB/(mA + mB)

Fundamental constants and conversion factors

h = 6.626x10-34Js
ao = 0.529x10-10 m c = 3.00x108 m/s
1 eV = 1.60x10-19 J me = 9.11x10-31kg
1 pm = 1.0x10-12 m

1 J = 1 kgm2/s2

Integrals
sin(nx/L)dx = (-L/n)cos(nx/L)
sin2(nx/L)dx = 0.5x - (L/4n)sin(2nx/L)
sin(nx/L)cos(nx/L)dx = (L/2n)sin2(nx/L)
8

More Old Exam Solutions