Pool of Questions: CHM 303

1. An electron is confined to a one-dimensional box 100 Å long. How many allowed energy
levels are there for this electron between 10 eV and 12 eV?
2. An electron is confined to a one-dimensional path of 10 Å length. Where in its path is the
electron most likely to be if it is in the state for which 𝑛𝑥 = 5?
3. The butadiene molecule, illustrated below is an example of a chemical system that, for
some purposes, can be approximated by the particle-in-a-box model. The four π-electrons
that are involved in the bonding between the p-orbitals of the carbon atoms can be
considered to be free to move over the whole length of the molecule. Though this is
obviously a three-dimensional problem, it can be approximated by considering the π-
electrons to be moving in a one-dimensional box whose length is the length of the molecule.
Make the further approximation that the molecule is linear (it actually exists in cis- and
trans- forms) and calculate the wavelength of the absorbed radiation when one of the π-
electrons undergoes a transition from the ground state of the molecule to the first excited
state (Hint: Only two electrons can be accommodated in each energy level).

H H H H
1.48  1.34 
H C C C C H

4. When discussing the free particle problem in terms of the particle-in-a-box model, there
would be difficulties with normalization of its wave function, why is this so?
5. The uncertainty principle can be expressed not only in terms of position and momentum,
but also other pairs of variables that are subject to the uncertainty relationship, such as
energy and time. Energy and time constitute an important pair, and their uncertainties can
be expressed as:
ℏ
∆𝐸∆𝑡 ≥
2
6. Here, the uncertainty in the time ∆𝑡 is the time associated with the measurement of the
energy. For time-independent phenomena, ∆𝑡 ⟶ ∞, which means that ∆𝐸 ⟶ 0; 1.e., the
energy is precisely defined, but we do not have the knowledge of time. This equation (
 ℏ
∆𝐸∆𝑡 ≥ 2), can be used to estimate the width of spectral lines since the lifetimes of excited

states are most often very short (i.e., ∆𝑡 is small). The effect of the uncertainty principle is
one reason for the broadening of spectral lines – the extent of this broadening can be
illustrated by the following problem: Estimate the minimum width of a spectral line
produced by a transition from the ground state of an atom (which in general has a long
lifetime) to an excited state with a lifetime of 5 × 10-9 sec.

7. Consider two eigenfunctions Ψ𝑖 and Ψ𝑗 of an operator 𝐴̂. If the eigenvalues associated

∫ Ψ𝑖∗ 𝐴̂Ψ𝑗 𝑑𝜏

8. Show that the operator for position of a particle, 𝑥̂, does not commute with the operator for
̂ . What is the significance of this? i.e., what conclusion can we draw from this
its energy 𝐻
result regarding the measurement of the position and energy of the particle?
9. A gaseous source emits light of wavelength 5 × 10-7 m. Assume that each molecule acts as
an oscillator of charge e and amplitude 10-10 m. (a) Compute the average rate of energy
radiation per molecule. (b) If the total rate of energy radiation of the source is 1 W, how
many molecules are emitting simultaneously?
10. Electromagnetic radiation from the sun falls on the earth’s surface at the rate of 1.4 × 103
W m-2. Assuming that this radiation can be considered as a plane wave, (a) estimate the
magnitude of the electric and magnetic field amplitudes in the wave and the momentum
density of the wave. (b) If this momentum is absorbed by the earth’s surface, compute the
radiation pressure of the earth.
̂ 𝜓 = 𝐸𝜓, that Eqs. 58 and 59
11. Show by direct substitution into the Schrӧdinger equation, 𝐻
are correct for this Hamiltonian.
12. Find the value of A to normalize the wave function 𝜓𝑛 = 𝐴 sin(𝑛𝜋𝑥 ⁄𝑎) within the
boundary 0 < x < a.
13. Calculate the minimum energy of an electron in a 1-bohr box and its wavelength. What
would be the momentum and the velocity of the electron? Show that the Heisenberg
uncertainty principle is obeyed in this system.
14. Calculate the energy difference between the n = 1 and n = 2 levels for an electron (m = 9.1
× 10-31 kg) confined to a one-dimensional box having a length of 4.0 × 10-10 m (this is the
magnitude of an atomic diameter). What wavelength corresponds to a spectral transition
between these levels?
15. Calculate the energy difference between the n = 1 and n = 2 levels for a marble of mass 1
g confined in a one-dimensional box of length 0.10 m. What wavelength corresponds to a
spectral transition between these levels?
𝑥2 𝑥2
16. What is the value of [ℎ̂, 𝐴̂]𝑓1 and [ℎ̂, 𝐴̂]𝑓2, where 𝑓1 (𝑥) = 𝑒 − 2 and 𝑓2 (𝑥) = 2𝑥𝑒 − 2
𝑥2 𝑥2
17. What is the value of [𝐴̂, ℎ̂]𝑓1 and [𝐴̂, ℎ̂]𝑓2, where 𝑓1 (𝑥) = 𝑒 − 2 and 𝑓2 (𝑥) = 2𝑥𝑒 − 2
18. If 𝐵̂ = 𝑥 + 𝑑̂, show that for [ℎ̂, 𝐵̂ ]𝑓2, 𝐵̂ is a lowering operator. Why do you think it is
referred to as a lowering operator with respect to 𝑓2 ?
19. What is the eigenvalue of 𝐵̂ 𝑓2 ? How does the result relate to 𝑓2 ?
20. Derive the commutator between ℎ̂ = 𝑥 2 − 𝑑̂2 and 𝐴̂ = 𝑥 − 𝑑̂ using a general function
𝑓(𝑥). Hint: Expand [ℎ̂, 𝐴̂] as a commutator equation that operates on f. Does this
commutator exist? If yes, what is the value?
21. Derive the commutator between ℎ̂ = 𝑥 2 − 𝑑̂ 2 and 𝐵̂ = 𝑥 + 𝑑̂ using a general function
𝑓(𝑥). Hint: Expand [ℎ̂, 𝐵̂ ] as a commutator equation that operates on f. Does this
commutator exist? If yes, what is the value?
𝑥2
22. Show that the function: 𝑓(𝑥) = 𝑥𝑒 −2 is an eigenfunction of ℎ̂ with eigenvalue = 3.
2
23. Show that 𝑒 −𝑥 is not an eigenfunction of ℎ̂.
24. Calculate the Rydberg constant for He+, assuming that the nuclear mass is the atomic
weight divided by Avogadro’s number. [ Answer: 109 722 cm-1, exact to 6 digits.]
25. Calculate the energy of the hydrogen atom in the lowest energy level – the first Bohr orbit.
26. Calculate the ionization potential (in eV) required to remove an electron in the ground state
of a hydrogen atom.
27. Calculate the wavelength of the line of the hydrogen atom for 𝑛1 = 2, 𝑛2 = 4. Repeat the
calculation for 𝑛2 = 9, 10, 11….. until it is evident that the series is approaching a limit.
What is this limit?
28. The coulombic potential between the nucleus (charge Ze) and an electron at a distance r is
 𝑍𝑒 2
𝑉 = − (4𝜋𝜖 for an electron in the first orbit. Calculate the total energy, the potential
0 )𝑟

energy, and the kinetic energy (which is the difference between the first two quantities).

29. Assuming that the sun is a spherical blackbody with a radius of 7 × 108 m, calculate the
sun’s temperature and the radiation energy density within it. The intensity of the sun’s
radiation at the surface of the earth (which is 1.5 × 1011 m distant from the sun) is 1.4 × 103
W m-2. Are the numbers evaluated realistic? Explain.
30. Find the energy and wavelength of a photon that can impart a maximum energy of 60 keV
to a free electron.
31. A beam of monochromatic x-rays with a wavelength of 10-11 m strikes a thin metal foil.
The scattered radiation is observed at angles of (a) 90° and (b) 60°. What two predominant
frequencies will be detected in each case?
32. The minimum light intensity that can be perceived by the eye is about 10-10 W m-2. How
many photons per second (wavelength 5.6 × 10-7 m) enter the pupil of the eye at this
intensity? The pupil area may be considered as 0.5 × 10-4 m2.
33. What is the effect on the energy levels of a one-dimensional potential box as the size of the
box (a) decreases? (b) increases?
34. Consider an electron in a one-dimensional potential box of width 2.0 Å. Calculate the zero-
point energy.
35. Calculate the zero-point energy of a neutron which is confined within a nucleus of size 10-
15
m.

Compiled by Dr. S. O. Sanusi (Kayode Sanusi)