Quantum Tutorial 3 (CML100)-Rotational Motion and Hydrogen Atom

1. Show that the spherical harmonics are eigenfunctions of the operator Lx2 + Ly2. (The proof is short.) What are
the eigenvalues?

2. Show by direct operation that the functions sin θ exp(iφ ) , sin θ exp(−iφ ) , and cos θ are eigenfunctions of
L̂z . What are the eigenvalues?

3. Confirm that the spherical harmonic Y10 is an eigenfunction of the Legendrian?

4. Compute the value of Lˆ2Y (θ , φ ) for the following functions: (a) 1 /(4π )1/ 2 (b) (3 / 4π )1 / 2 cos θ (c)
(3 / 8π )1/ 2 sin θ exp(iφ ) .]

5. In the far infrared spectrum of H79Br, there is a series of lines separated by 16.72 cm–1. Calculate the values
of the moment of inertia and the internuclear separation in H79Br. [3.35 x 10-47 kgm2; 142 pm]

6. Calculate the moment of inertia of H35Cl, H37Cl, and D35Cl all of which have an equilibrium bond length of
1.275 Å. Calculate the positions of the first three rotational transitions for H35Cl, H37Cl, and D35Cl.

7. The J=0 to J=1 transition for Carbon Monoxide (CO) occurs at 1.153 x 105 MHz. Calculate the value of the
bond length for CO. [113 pm]

8. This problem deals with angular momentum operators and spherical harmonics. You are given two operators
L̂+ and L̂− that can be written as Lˆ+ = Lˆ x + iLˆ y and Lˆ− = Lˆ x − iLˆ y with L̂x and L̂ y being the angular
momentum operators in the x and y directions respectively.
(a) Express ‘ Lˆ+ Lˆ− + Lˆ− Lˆ+ ’ in terms of L̂2 and Lˆ2z with L and Lz having their usual meaning. You may use
any of the known commutation relations discussed in the class.
(b) Are spherical harmonics eigenfunctions to [ Lˆ + , Lˆ − ] ? If no, why not? If yes, what are the eigenvalues.
(c) If a system is in the state described by the wavefunction Yl ,ml (θ , ϕ ) , find Lx . Use the following
relations: Lˆ +Yl ,m (θ , ϕ ) = c+Ylm +1 (θ , ϕ ) and Lˆ−Yl ,m (θ , ϕ ) = c−Yl ,m −1 (θ , ϕ ) where c+ and c– are constants.
l l l l

9. The following functions are examples of spherical harmonics: Y1(θ,φ) = N1sin2θcosθexp(±2iφ) and Y2(θ,φ) =
N2(5cos3θ – 3cosθ). Deduce the quantum numbers which characterize these spherical harmonics.

10. For angular momentum with quantum number l = 3, how many m-values are there? What is the semi-angle of
the cone subtended by the angular momentum vector if its z-projection is 2h ?

11. A hydrogen-like atom can be formed from a proton and a negative muon whose mass is approximately 206
times that of the electron. What are the energies for the 1s and 2p levels of this atom?

me e 4
12. Show explicitly that Hψ = − ψ for the ground state of a hydrogen atom.
8ε 02 h 2

13. For a hydrogen atom in the ground state find the classically forbidden region and calculate the probability of
finding the electron in this region.
14. Calculate the probability that an electron described by a hydrogen 1s wavefunction will be found within one
bx ⎛ x
2
2x 2 ⎞
Bohr radius of the nucleus. Use the integral: ∫ x e dx =e ⎜ − 2 + 3 ⎟⎟
2 bx
⎜ [0.323]
⎝ b b b ⎠
15. Calculate the most probable distance (i.e., radius) at which the 1s electron of H-like atom with atomic number
Z is to be found. Show that as Z increases, this most probable distance decreases. ψ1s = (Z3/πa03)1/2e–Zr/a0.

16. Find the average distance of 1s electron from the nucleus in hydrogen atom for which, ψ1s = 1/(πa03)1/2e–r/a0.

17. We have seen before that any linear combination of eigenfunctions of a degenerate energy level is an
eigenfunction of the Hamiltonian with the same eigenvalue. In this regard, the 2px angular orbital can be
Y (θ , φ ) − Y1, −1 (θ , φ )
defined as: ψ 2 px = − 1,1 . (a) Show that ψ 2 px is normalized. (b) Is ψ 2 px an eigenfunction of
2
L2? If so, what is the corresponding eigenvalue? (c) Is ψ 2 px an eigenfunction of Lz? If so, what is the
corresponding eigenvalue?

18. Show that the hydrogenlike atomic ψ 210 is normalized and orthogonal toψ 200 .

19. Prove that <V> = 2<E> for a 2s electron.

20. If we ignore the inter-electronic repulsion in helium, what would be its ground state energy and wave
function? The experimental ground state energy of He is -79.0 eV.

21. Show where the two maxima in the plot of r 2ψ 22s (r ) against r occur?

22. Consider the following total wavefunctions of the following hydrogen-like orbitals. Identify the n, l and ml
values and hence the respective orbital:
3
1 ⎛ Z ⎞ −ρ 2
2
5
(i) Ψnlm (r ,θ , φ ) = ⎜⎜ ⎟⎟ e (6 − ρ )ρ 2 (3 cos 2 θ − 1)
l
16π 96 5 ⎝ a0 ⎠
3
5 1 ⎛ Z ⎞ 2 −ρ 2
(ii) Ψnlm (r ,θ , φ ) = ⎜⎜ ⎟⎟ e (6 − ρ )ρ 2 sin 2 θe 2 iφ
l
32π 96 5 ⎝ a0 ⎠
3
5 1 ⎛ Z ⎞ −ρ 2 2
2

(iii) Ψnlm (r ,θ , φ ) = ⎜⎜ ⎟⎟ e ρ sin θ cos θe −iφ

(iv) Ψnlm (r ,θ , φ ) = ⎜⎜ ⎟⎟ e (6 − 6 ρ + ρ 2 )
l
4π 9 3 ⎝ a0 ⎠

23. Make sure that you know how to draw schematically the wavefunctions of the radial wave functions and the
radial probability distribution functions, taking care of the number of radial nodes
24. For an isolated hydrogen atom, why must the angular momentum vector L lie on a cone that is symmetric
about the z-axis. Can the angular momentum vector evr point exactly along the z-axis? Why? (Hint: Recall
our discussion on space quantization).

3a0 6a0
25. Prove that the average value of r in the 1s and 2s states of a hydrogenic atom is and respectively.
2Z Z
26. The average values of 1/r, 1/r2 and 1/r3 for a hydrogen-like atom can be evaluated in general and are given by:

1 Z
=
r a0 n 2
1 Z2
=
r2 ⎛ 1⎞
nl
a02 n3 ⎜ l + ⎟
⎝ 2⎠
1 Z3
=
r3 ⎛ 1⎞
nl
a02 n 3 ⎜ l + ⎟(l + 1)
⎝ 2⎠

Verify these expressions explicitly for the ψ210 orbital.

27.

Some useful integrals you might need are provided below:

∞ ∞ ∞ ∞
1 1 6 n!
(i) ∫ r exp(−br )dr = 2 (ii) ∫ r exp(−br )dr = 3
2
(iii) ∫ r exp(−br )dr = 4 (iv)
3
∫x
n
exp(−ax)dx =
0
b 0
b 0
b 0
a n+1