2025-2026 Semester II. CML1001. Tutorial 3.
1. Show that the function exp(-bx2) satisfies the Schrödinger equation for the quantum harmonic
oscillator. What conditions does this place on b? What is the energy, E?
2. Show that 𝜓! (𝑥) and 𝜓" (𝑥) are normalized where 0 and 1 are the respective vibrational quantum
numbers.
3. Show explicity that 𝜓! (𝑥) is orthogonal to 𝜓" (𝑥), 𝜓# (𝑥) and 𝜓$ (𝑥)for the harmonic oscillator.
1/ 4
æ 4a 3 ö 1
4. (a) Is y 1 ( x) = çç ÷÷ x exp[- ax 2 ] an eigenfunction of the kinetic energy operator where
è p ø 2
a = kµ 2 . (b) What are the average values of kinetic and potential energies for a quantum
!
mechanical oscillator in this state.
5. (a) Calculate <x>, <px> and <x2> and 〈𝑝%# 〉 for a harmonic oscillator for the ground state n = 0?
Standard integrals have been provided at the end of the assignment. (b) Examine the uncertainty
principle ∆𝑥∆𝑝% for the harmonic oscillator in this state.
6. A strong absorption band of infrared radiation is observed for 1H35Cl at 2991 cm-1. (a) Calculate the
force constant, k, for this molecule. (b) By what factor do you expect the frequency to shift if H is
replaced by D? Assume the force constant to be unaffected by this substitution. [516.3 Nm-1; 0.717]
7. The Hamiltonian of a 2-dimensional (2-D) isotropic (having the same value of k in all directions)
! æ¶ 2
¶ ö 12 2
harmonic oscillator has the form H =- ç + ÷ + mw ( x + y ) . 2 2 2
(a)
2m è ¶x ¶y ø 2 2 2
Write an expression for the wave function for the of the 2-D oscillator. (b) What is the energy
eigenvalue for this system? (c) What is the zero point energy? (d) Find a general expression for the
degeneracy of the energy levels.
8. Consider a particle confined to the right hand half of a harmonic oscillator potential with V(x) = ∞ for
x < 0 and V(x) = 0.5kx2 for x ≥ 0. Compare the allowed wavefunctions for this system with those of
a normal harmonic oscillator having the same values of m and k. what are the allowed energies of this
half-oscillator. (Will be done in class!)
9. Intensity of spectroscopic transitions between the vibrational states of a molecule are proportional to
the square of the integral ∫ Ψν’ x Ψν dx over all space. Show that the only permitted transitions are those
for which ν’= ν ± 1 and evaluate the integral.
10. In the infrared spectrum of H79Br, there is an intense line at 2559 cm-1. Calculate the force constant of
H79Br and the period of vibration of H79Br.
! 1 3! 2
11. It can be proved generally that x 2 = (u + ) and x 4
= (2u 2 + 2u + 1) for a harmonic
(µk )1/ 2
2 4µk
oscillator. Verify these for the first 2 states of a harmonic oscillator.
12. The maximum potential energy that a diatomic molecule can store is ½ kx2, where x is the amplitude
of the vibration. If the force constant is 1.86 × 103 N m-1, calculate the maximum amplitude of vibration
for the CO molecule in the ground vibrational state.
13. (a) Derive the expression for the standard deviation of the bond length of a diatomic molecule when
it is in its ground state. (b) What percentage of the equilibrium bond length is this standard deviation
for CO in its ground state? For CO, n~ = 2170 cm-1 and Re = 113 pm. [2.98 %]
14. Find the nodes of the wavefunction for the v = 4 state of a harmonic oscillator described by
y = N (16x - 48x + 12) exp(- x 2 ) , where 𝝃 = 𝒙√𝜶 . Sketch the wavefunction
2
4 2
4 4
of this state and write the expression for the probability of the particle tunneling into the classically
forbidden region.
15. Moment of inertia for rigid rotator is defined as 𝐼 = 𝑚" 𝑙"# + 𝑚# 𝑙## . Show it is equivalent to writing
" " "
𝐼 = 𝜇𝑙 # , where 𝑙 = 𝑙" + 𝑙# and 𝜇 the reduced mass given by = +
& '! '"
16. Normalize 𝑇(𝜙) = 𝐴' 𝑒 (')
17. Show that 𝑌"*" (𝜃, 𝜙) is not an eigenfunction of 𝐿;% .
18. Show that 𝐿;# and 𝐿;+ commute.
19. A measurement yields √2ℏ for the magnitude of a particle's orbital angular momentum. If 𝐿% is now
measured, what are the possible outcomes?
20. Verify the orthogonality of the 𝑝% , 𝑝, , 𝑎𝑛𝑑 𝑝+ functions.
21. Express the real 𝑑 functions given in the book as linear combinations of the complex functions
𝑑# , 𝑑" . . . , 𝑑*# .
22. Show that C𝐿;% , 𝐿;, D = 𝑖ℏ𝐿;+ (Hint: Use the operator in Cartesian coordinates).
23. Show that C𝐿;% , 𝑦D = 𝑖ℏ𝑧
24. Show by direct operation that the functions sin 𝜃 exp 𝑖𝜙 , sin 𝜃 exp(−𝑖𝜙) , and cos 𝜃 are
eigenfunctions of 𝐿;+ . What are the eigenvalues?
25. Use the operator for 𝐿;# in polar coordinates to show that the function (3 cos # 𝜃 − 1) is an
eigenfunction of this operator. What is the eigenvalue? What is the quantum number 𝑙 for this
function?
26. Show that 𝑌"*" (𝜃, 𝜙)is normalized and it is orthogonal to 𝑌#" (𝜃, 𝜙).
27. 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 and D35Cl.
28. In the far infrared spectrum of H79Br, there is a series of lines separated by 16.72 cm*" . Calculate
the values of the moment of inertia and the internuclear separation in H79Br.
29. The 𝐽 = 0 → 𝐽 = 1 line in the microwave absorption spectrum of 12C16O and of 13C16O was found
to be at 3.84235 cm*" and 3.67337 cm*" . Calculate (a) the bond length of 12C16O, (b) the relative
atomic mass of 13C.
Useful Relations and Integrals
General
Wavefunction of Harmonic Oscillator:
"/
−𝛼𝑥 # 1𝛼 "/. 𝑘𝑚 .
𝜓- (𝑥) = 𝑁- 𝐻- _𝑥 √𝛼a exp b c2 d ; 𝑁- = b d ; 𝛼 = h j
√2- 𝑛! 𝜋 ℏ#
𝝃 = 𝒙√𝜶
Relations of Hermite Polynomials:
𝑑𝐻- (𝑧)
𝐻-0" (𝑧) = 2𝑧𝐻- (𝑧) − 2𝑛𝐻-*" (𝑧) ; = 2𝑛𝐻-*" (𝑧) ;
𝑑𝑧
𝑑 - *+ "
"
𝐻- (𝑧) = (−1)- 𝑒 + 𝑒
𝑑𝑧 -
2
∫*2 𝐻-# (𝑧)𝐻- (𝑧)𝑒𝑥𝑝(−𝑧 # )𝑑𝑧 = √𝜋 2- 𝑛!; 𝑓𝑜𝑟 𝑛1 = 𝑛