University of Groningen

Faculty of Science and Engineering

BSc Chemistry and Chemical Engineering

Spectroscopy 2024-2025
Student Tutorial Questions

Lecturers: W.R. Browne, M. Tromp. T. R. Canrinus.

Questions compiled by A. Volker, S. Rooijmans, M. Fiechter, W.R.

Browne, and A. S. Sardjan

Date: April 12, 2025

Tutorial 3
1. For each of the following operators determine whether or not the wavefunction ψ = sin ax
is an acceptable solution. Briefly justify your answer.
(a) The linear momentum operator

h d
p̂ =
2πi dx

(b) The Hamiltonian operator in a region of zero potential energy

h2 d2
H=T+V= + V(x)
8π 2 m dx2

Solution:
(a)
h d h d sin ax ha
ψ= = cos ax
2πi dx 2πi dx 2πi
therefore not an acceptable solution since ψ is not recovered.

(b) The fact that V (x) is zero means that the term can be dropped. The double
differential of sin ax give sin ax back again so it is acceptable

2. For each of the following operators determine whether or not the wavefunction:
ψ = a i sin kx
is an acceptable solution. Briefly justify your answer.
(a) The position operator x̂
(b) The linear momentum operator p̂ = h d
2πi dx

Solution:
(a) x̂ = x× therefore

x̂(ψ) = x̂(ai sin kx) = x × ai sin kx = xai sin kx

xa i sin kx contains the original function ψ = ai sin kx however if you think about
it a bit deeper then you realise that x is a variable and hence the function you
get back is actually xai sin kx which is not the original function.

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 (b) p̂ = h d
2πi dx therefore

h d(ai sin kx) h hk hk

p̂(ψ) = p̂(ai sin kx) = = kai cos kx = a cos kx a cos kx
2πi dx 2πi 2π 2π
does not contain the original function ψ = ai sin kx
hk
2π is a real single valued number which is satisfies the criterion for an eigenvalue
of a Hermitian function, however and is not an acceptable solution (eigenvalue)
as the eigenfunction is not returned.

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 3. Which of the following are solutions to the operator for momentum? Justify your
answers in terms of the recovery of an eigenfunction and a proper eigenvalue.

̵ d
p̂ = −ih
dx

(c) sin(kx ± ωt) (d) cos(kx ± ωt)

2)
(a) ei(kx−ωt) (b) eiωt sin kx (e) ei(ky−ωx

Solution:
(a)
̵ d i(kx−ωt) ̵ ⋅ ikei(kx−ωt) = hke
̵ i(kx−ωt)
−ih e = −ih
dx
so this is a solution with a single valued eigenvalue and the function.

(b)
d ̵ iωt sin kx) = −ihke
̵ iωt cos kx = −ihke
̵ iωt cos kx ≠ Eψ
(−ihe
dx
not a proper solution

(c)
d̵ ̵ ⋅ ±ω cos(kx ± ωt)
−ih sin(kx ± ωt) = −ih
dt
which cannot be written as a constant times the original function (the sine)
hence it is not a solution.

(d) Similar to c), not a solution either.

(e)
2)
ei(ky−ωx

the derivative of an exponential returns the exp but the 2x also so not single
valued

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 4. In the following two equations identify the:

(i) Operator, (ii) wavefunction, (iii) eigenvalue, and (iv) eigenfunction

(a)
h2 d2 (sin ax − cos ax) a2 h2 cos ax a2 h2 sin ax
− = − +
8π 2 m dx2 8π 2 m 8π 2 m
(b)
h d sin ax h cos ax
=−
2πi dx 2πi

Solution:
(a) (i) − 8πh2 m dx 2 , (ii) ψ = sin ax − cos ax. Since the wavefunction is returned it is
2d 2

h2 a2
also an eigenfunction. The eigenvalue is 8π 2 m , which is real and single-valued
so acceptable as eigenvalue for a Hermitian function.

(b) In this one there is no acceptable eigenfunction and therefore no eigenvalue,

h d
but the wavefunction is sin ax, the operator is 2πi dx but it should have returned
ha cos ax
2πi but this is not real anyhow

Some calculation exercises to keep you mathematically fit (remember no units and di-
mensional analysis means you don’t get marks in the exam!!!

5. What is the minimum uncertainty in the position of a bullet of mass 5.0 g that is known
to have a speed somewhere between 350.00001 and 350.00000 m s−1 ? Can we actually
measure so precisely? We might cover the uncertainty principle next week but you can
look ahead in chapter 6 if you are not certain how to do this one ;-)
The following questions require discussion answers and give you a good idea of questions
to be expected in the exams.

6. Explain using diagrams why the wavefunction for a particle in a circle requires that
energies are quantised (hint: consider a standing wave).

Solution: The standing waves must have wavelengths for which they do not in-
terfere destructively on the second cycle. The concept of interference should be
mentioned

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 7. The Rayleigh-Jeans law was able to predict the black body emission spectra in the long
wavelength region. Explain why, by considering the equation, it fails to predict the
short wavelength emission spectrum of a black body.

Solution: The Rayleigh-Jeans law. dE/dλ = ρ where ρ(λ, T ) = 8πkB T /λ4 predicts
that the rate of change of Energy with wavelength increases as the wavelength de-
creases. - Ultraviolet catastrophe.
It fails because it assumes the equipartition theory holds for all energies but it
doesn’t for vibrational and electronic levels

8. Describe briefly the photoelectric effect in terms of the concept of a work-function and
quantisation.

Solution: The issue of quantisation i.e. beyond the work function photon energy
makes no difference to number of electrons but intensity does implies one photon
gives one electron etc.

9. What a meant by the term ’orthogonal wavefunctions’?

Solution: Wavefunctions for which their product integrated over all space is equal
to zero.

The next questions relate to expectation (what would the average result be after lots of
measurements etc)

10. The lowest energy electrons of a carbon nanotube can be described by the normalised
wavefunction

√
⎛ 2⎞ πx
sin ( )
⎝ L⎠ L

where L is the length of the nanotube. What is the probability of finding the electron
between x = L/4 and x = L/2

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 Solution: Probability density
L/2 2 L/2
= ∫ ψ ∗ ψdx = ∫ (2/L)1/2 (sin(πx/L) dx = ∫ (2/L) (sin2 (πx/L)dx = 0.409 .
L/4 L/4

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