PX3820

THE UNIVERSITY OF WARWICK

THIRD YEAR EXAMINATION: April 2022

QUANTUM PHYSICS OF ATOMS - SOLUTIONS

Answer all questions

Time Allowed: 1.5 hours

Read carefully the instructions on the answer book and make sure that the particulars required
are entered on each answer book.
The nominal mark assigned to each part of a question is indicated by means of a bold figure
enclosed by curly brackets, e.g. {2} , immediately following that part. This mark scheme is
for guidance only and may be adjusted by the examiner.

Calculators may be used for this examination

PX3820 1 (Continued)
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Standard integrals:

R ∞ n −bx n!
0 x e dx = bn+1 where b > 0 is a constant and n is a positive integer.

sin2 xdx = π/2, sin3 xdx = 4/3, sin4 xdx = 3π/8, and sin5 xdx = 16/15.
Rπ Rπ Rπ Rπ
0 0 0 0

R 2π R 2π ±iφ
0 sin φ cos φ dφ = 0 and 0 e sin φ cos φ dφ = 0.

R 2π +2iφ
sin φ cos φ dφ = +iπ/2 and 02π e−2iφ sin φ cos φ dφ = −iπ/2.
R
0 e

PX3820 2 (Continued)
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Solutions to Quantum Physics of Atoms

Time allowed: 1.5 hours

ANSWER ALL QUESTIONS

1. a) This is an unseen problem although the method and several examples are discussed
in the module.
(i) The ground-state has the lowest energy. In this case the ground state energy is
E0 when n = 1. 1 mark.
(ii) The first-order shift En1 is given by

En1 = hn | V̂ | ni. 1 mark.

Using the information given, the first-order shift in the energy of the state with
n = 4 is 16λ E0 . 2 marks.
(iii) The second-order shift in the energy En2 is given by
2
hp | V̂ | ni
En2 =− ∑
. 2 marks.
p E p0 − En0
p6=n

Using the information given, the second-order shift in the state with n = 2 is
( )
2 2
|2λ E 0 | |6λ E 0 |
En2 = − + ,
(E0 − 2E0 ) (3E0 − 2E0 )
 2 2
4λ E0 36λ 2 E02

= − + ,
−E0 E0
= −32λ 2 E0 . 2 marks.

b) This is an unseen problem although the method and several examples are discussed
in the module.
(i) A = h1, −1| V̂ |1, −1i and D = h1, +1| V̂ |1, +1i both equal zero. For example,

A = h1, −1| V̂ |1, −1i ,

Z
= R∗21 (r)Y1−1
∗
(θ , φ ) xy f (r) R21 (r)Y1+1 (θ , φ ) d 3 r,

(replace xy) x = r sin θ cos φ and y = r sin θ sin φ ).

Z
= R∗21 (r)Y1−1
∗
(θ , φ ) r sin θ cos φ r sin θ sin φ f (r) R21 (r)Y1+1 (θ , φ ) d 3 r.
Z 2π Z 2π
−iφ +iφ
This contains the integration e e sin φ cos φ dφ = sin φ cos φ dφ = 0.
0 0
So A = D = 0. 1 mark.

PX3820 3 (Continued)
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B = h1, −1| V̂ |1, +1i ,

Z
= R∗21 (r)Y1−1
∗
(θ , φ ) xy f (r) R21 (r)Y1+1 (θ , φ ) d 3 r,

(replace xy) x = r sin θ cos φ and y = r sin θ sin φ ),

Z
= R∗21 (r)Y1−1
∗
(θ , φ ) r sin θ cos φ r sin θ sin φ f (r) R21 (r)Y1+1 (θ , φ ) d 3 r,

(collect terms in r, θ , φ ),
Z
= ∗
R∗21 R21 (r) r2 f (r)Y1−1 sin2 θ sin φ cos φ (r)Y1+1 d 3 r,
∗
(write d 3 r = r2 sin θ drdθ dφ and add the limits and the expressions for Y1−1 , and Y1+1 ),
Z 2π
−3
Z Z π
2 4
= [R21 ] r f (r) dr 5
sin θ dθ sin φ cos φ e+2iφ dφ ,
8π 0 Z0
(using standard integrals and writing [R21 ]2 r4 f (r) dr = 5R),
−3 16
= 5R × × × iπ/2 = −iR.
8π 15
Then C = +iR. 3 marks. (For completeness in the solution),

C = h1, +1| V̂ |1, −1i ,

Z 2π
−3
Z Z π
= [R21 ]2 r4 f (r) dr sin5 θ dθ sin φ cos φ e−2iφ dφ ,
8π 0 Z0
(using standard integrals and writing [R21 ]2 r4 f (r) dr = 5R),
−3 16
= 5R × × × −iπ/2 = +iR.
8π 15
(ii) Solving the secular equations gives

−∆E 1 0 0 0
0 −∆E 1 0 0
= 0, 2 marks.
0 0 −∆E 1 −iR
0 0 +iR −∆E 1
So ∆E 1 = 0, R and −R. 1 mark.
(iii) The unshifted level ∆E 1 = 0 is two-fold degenerate, while the other two levels

are one-fold degenerate. 2 marks.

c) This is a new problem. The method and several examples were discussed in the
module.
(i) The trial wavefunction has the form ψT = Az exp(−β z). For the normalisation
of ψT . Z ∞ Z ∞
ψT∗ ψT dz = A2 z2 exp(−2β z)dz. 1 mark.
0 0

PX3820 4 (Continued)
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Using standard integral

2!
A2 = 1.
(2β )3

giving

A2 = 4β 3 or A = 2β 3/2 . 1 mark.

(ii) The energy is given by

−h̄2 d 2
Z ∞  
2
E =A z exp(−β z) + mgz z exp(−β z)dz. 1 mark.
0 2m dz2

To calculate the energy E evaluate each term separately. The kinetic term is
given in the question.

The potential term gives

3!
Z ∞
2
A mgz3 exp(−2β z)dz = A2 mg ,
0 (2β )4
3mg
= . 2 marks.
2β
β 2 h̄2
Combining these two gives E = 2m + 3mg
2β .
(iii)

dE 2β h̄2 3mg
= − 2 = 0,
dβ 2m 2β
2
β h̄ 3mg
= ,
m 2β 2
3m2 g
β3 = . 2 marks.
2h̄2
Putting this result back in to E gives
2/3 2 −1/3
3m2 g 3mg 3m2 g
 
h̄
E = + , 1 mark.
2h̄2 2m 2 2h̄2
"  1  1 #
9 31 3 2 3 2 1 2
= + h̄ 3 m 3 g 3 ,
4 2 2 3
 1  1
9 3 1 33 2 1 2
= h̄ 3 m 3 g 3 .
2 2 2

PX3820 5 (Continued)
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2. a) (i) This is a problem but others like it are solved in the notes.
Hund’s rules
(1) First maximise total spin. That is S = (∑i msi )max .
(2) Then maximise the sum of the orbital angular momentum components ∑i mli
subject to the Pauli Exclusion Principle. That is L = (∑i mli )max .
(3) For a shell that is less than 12 full the ground state configuration is when J is
a minimum i.e. J = |L − S| .
For a shell that is more than 12 full the ground state configuration is when J is a
maximum i.e. J = |L + S| .
For a shell that is exactly 12 filled the ground state configuration is L = 0, J = S.
3 marks.
So nitrogen has S = 3/2, L = 0 and J = S = 3/2 giving 2S+1 SJ =4 S 3 . 2 marks.
2
(ii) This level is (2S + 1)(2L + 1) = 4 × 1 = 4-fold degenerate. 1 mark.
We can lift the degeneracy by applying a magnetic field B. 1 mark.
The splitting of the levels with B along z is
∆E (L, S, ml , ms ) = L, S, ml , ms | V̂mag | L, S, ml , ms
= µB Bz (ml + 2ms ). 2 marks.
+3 +1 −1 −3
In this case ms = 2 , 2 , 2 , 2 with ml = 0. 1 mark.
b) (i) All bookwork. I will accept an answer in note form.
Within a laser cavity, the number of photons N (ν) with frequency ν, and the
same wave vector k and polarization λ , will increase with time due to stimulated
and spontaneous emission. If the number of emitting atoms in the upper level is
Ni then this rate of emission involves the spontaneous single photon transition
rate Ri j multiplied by [N (ν) + 1].
dN + (ν)
= Ni [N (ν) + 1] Ri j .
dt
There is also a decrease in the number of photons due to stimulated absorption
proportional to the number of absorbing atoms, N j , the spontaneous single pho-
ton transition rate, Ri j , and N (ν)
dN − (ν)
= N j N (ν) Ri j ,
dt
(For completeness students may also mention that there is a loss of photons due
to leakage from the cavity proportional to the number of photons N (ν). This
loss has some time constant τ0 that is made as large as possible. But there are no
marks lost if this is not mentioned.) So the net change in the number of photons
is
dN (ν) N (ν)
= Ni [N (ν) + 1] Ri j − N j N (ν) Ri j −
dt τ0
 

1
= N (ν) Ni − N j Ri j − + Ni Ri j . 3 marks.
τ0

PX3820 6 (Continued)
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OR Einstein considered three kinds of process in which photons with energy

hν are absorbed or emitted between states i and j with energies Ei and E j


Ei − E j = hν ; an absorption of photons by atoms that is proportional to the
intensity of light with proportionality constant B ji , an emission of photons by
atoms that is proportional to the intensity of the light (induced or stimulated
emission) with proportionality constant Bi j , and a spontaneous emission of pho-
tons, independent of light with a probability Ai j .
In thermal equilibrium at a temperature T , with a certain number of atoms N j
and Ni in states j and i, the total number of atoms going from j to i per second is

R j→i = N j B jiU (ν, T ) ,

while the number going from i to j per second is

 
Ri→ j = Ni Ai j + Bi jU (ν, T ) .

where U (ν, T ) is the spectral energy density at a frequency ν and temperature

T. 3 marks.

OR Consider a system of atoms with two energy levels Ei and E j where Ei > E j
in a laser cavity where the number of photons N (ν) with frequency ν. If the
number of emitting atoms in the upper level is Ni then the rate of emission rate
is
dN + (ν)
= Ni N (ν) Bi j + Ni Ai j .
dt
where Ai j and Bi j are related to the spontaneous and stimulated transition rates,
respectively.
There is also a decrease in the number of photons due to absorption proportional
to the number of absorbing atoms, N j , the absorption transition rate, B ji , and
N (ν)
dN − (ν)
= N j N (ν) B ji
dt
and a loss of photons due to leakage from the cavity proportional to the number
of photons N (ν). This loss has some time constant τ0 that is made as large as
possible.
So the net change in the number of photons is
dN (ν) N (ν)
= Ni N (ν) Bi j + Ni Ai j − N j N (ν) B ji − ,
dt τ0
 

1
= N (ν) Ni − N j Bi j − + Ni Ai j ,
τ0
where we have assumed Bi j = B ji . 3 marks.

PX3820 7 (Continued)
PX3820

(ii) From above the number of photons will decrease with time unless Ni > N j .
1 mark.
In thermal equilibrium

Ni e−Ei /kT
= −E /kT = e−(Ei −E j )/kT = e−hν/kT ,
Nj e j

which is always smaller than 1 and so Ni will be less than N j . 1 mark.

If we could arrange by some non-thermal method to have a system in which
the number of atoms Ni in the higher energy state i, is much greater than the
number N j in lower energy state j, (population inversion), then any photons of
energy hν will not be strongly absorbed, because there are a small number of
atoms in state j. This light will induce or stimulate emission of more light of the
same frequency, phase, polarization and direction of propagation, via transitions
from Ei to E j . Thus for laser action we must create an excess population in
the upper level - population inversion - and operate in non-equilibrium mode.
2 marks.
c) A mixture of a new problem and bookwork.
(i) Normalization requires |ca |2 + |cb |2 = 1. 1 mark.
(ii) Substitute the values for cb (0) = m into the equation gives, to first-order,
(1)
ih̄ċa (t) = Vab (t) exp (−iω0t) cb (0) ,
= Vab (t) exp (−iω0t) m. 2 marks.

Integrating from t = 0 to τ subject to the initial condition ca (0) = n.

im
Z τ
(1)
ca (τ) = n − Vab (t) exp (−iω0t) dt. 2 marks.
h̄ 0

(iii) In the absence of any perturbation each component evolves with its exponential
factor,

Ψ (t) = ca ψa exp (−iEat/h̄) + cb ψb exp (−iEbt/h̄) . 1 mark.

Measuring the energy of this state gives either Ea or Eb . For this state the expec-
tation value of some quantity hpit is given by

hpit = |ca |2 Paa + |cb |2 Abb + c∗a cb Pab e−iω0t + c∗b ca Pba eiω0t
= |ca |2 Paa + |cb |2 Pbb + 2ℜe c∗a cb Pab eiωt
 

where Pab = hψa | P̂ |ψb i. So the expectation value hpit oscillates (with a period
2π 2 2 ∗
T = |ω | ) between the values |ca | Paa + |cb | Pbb ± 2 [ca cb Pab ]. 2 marks.
0

PX3820 8 END