CML100: Quantum Chemistry - Exercise Sheet 2

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 exp(i ) , sin exp( i ) , and cos are eigenfunctions of
L . What are the eigenvalues?
z

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

4. Compute the value of L2Y ( , ) for the following functions: (a) 1 /( 4 )1/ 2 (b) (3 / 4 )1/ 2 cos (c)
(3 / 8 )1/ 2 sin exp(i ) .

5. Prove that L2 commutes with L x , L y and L z but the individual angular momentum components are non-
commuting. Use Cartesian coordinates for the commutation of L , L and L problem. Do you see a pattern
x y z

in this formula?

6. The following functions are examples of spherical harmonics: Y1(,) = N1sin2cosexp(2i) and Y2(,) =
N2(5cos3 3cos). Deduce the quantum numbers which characterize these spherical harmonics.

7. 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 2 ?

8. 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
9. Show explicitly that H 2 2 for the ground state of a hydrogen atom.
8 0 h

10. For a hydrogen atom in the ground state find the classically forbidden region and calculate the probability of
finding the electron in this region.

11. Calculate the probability that an electron described by a hydrogen 1s wavefunction will be found within one
x2 2x 2
Bohr radius of the nucleus. Use the integral: x 2 ebxdx ebx 2 3 [0.323]
b b b
12. 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 increase, this most probable distance decreases. 1s = (Z3/a03)1/2eZr/a0.

13. Find the average distance of 1s electron from the nucleus in hydrogen atom for which, 1s = 1/(a03)1/2er/a0.

14. Show that the hydrogenlike atomic 210 is normalized and orthogonal to 200 .

15. Prove that <V> = 2<E> for a 2s electron. This is called virial theorem.

16. 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.
17. Show where the two maxima in the plot of r 2 22s (r ) against r occur?

18. Prove variational theorem assuming a trial wavefunction that is an approximation to the true wavefunction
o by expressing formally as = cn n , where cn are constants.
n
19. Use a trial wavefunction of the form exp(r) to calculate the ground-state energy of a hydrogen atom.

20. In LCAO-MO treatment, which term explains the bonding in molecules and why?

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 n1