CHEM 646 Physical Chemistry I, Spring 2010

Problem Set #5

Problems from Text:

Chapter 5
Problems: 24

Additional Problems

1. The spin-1/2 eigenfunctions |α > and |β > cannot be expressed in terms of

spherical harmonics, but they can be expressed as column matricies

é1 ù é0 ù
| a = ê ú and | b = ê ú
ë0 û ë1 û

The components of the spin operator can be represented by the following

matrices:

h é0 1ù h é0 iù h é1 0ù
Söx = ê ú; Söy = ê ú; Söz = ê ú
2 ë1 0û 2 ëi 0û 2 ë0 - 1û

(a) Show that the angular momentum commutation relations are satisfied for
these matrices.

(b) Show that |α > and |β > are eigenfunctions of S

ö and ö2 .
z S

2. Calculate the angles that a spin angular momentum vector for an individual
electron can make with the z axis.

3. Why is the s, p, d,… nomenclature, which was derived for the H atom, also valid
for many-electron atoms?
1 2
4. Consider the harmonic oscillator of mass m with potential energy V (x) = k x .
2
Using a trial ground-state wavefunction of the form ψ ( x;a ) = e Ða x 2
, use the
variational theorem to determine (a) the optimal value of α and (b) the
corresponding ground-state energy. (c) Compare your answer in (b) to the exact
ground-state energy E = 1/2 hv , where ν = k / m . What does this comparison
tell you about your optimal variational wavefunction?

5. Use the variational method with a trial wavefunction ψ (r,q ,f ;a ) = e Ða r to

2

estimate the ground state energy of the hydrogen atom.

6. Positronium consists if an electron and a positron (positive particle with the same
mass as the electron). (a) Calculate the wavelength of the radiation emitted when
the system goes from the n = 2 energy level to the n = 1 energy level. (b)
Calculate the ionization energy.

7. The outer electron of an alkali atom may be treaded in an approximate way, as if

it were in a hydrogenic s orbital. Suppose that one takes the quantum number for
the outer electron to be 2, 3, 4, 5 and 6, respectively for Li, Na, K, Rb and Cs.
What value of Z must be given to account for the observed first ionization
energies of these atoms? Explain why they differ from unity.

8. Write the Slater determinant for the ground-state configuration of Be.

9. In this problem, you will show that the electron probability density of the filled 2p
(n = 2, l = 1) subshell is spherically symmetrical and that therefore the total
angular momentum is zero. The angular distribution of the electron probability
density is simply the sum of the squares of the manitude of the angular part of the
wavefunctions for l = 1 and ml = -1, 0 and 1.

(a) Write an expression for

2 2 2
F (q ,f ) = Y1,- 1 (q ,f ) + Y1,0 (q ,f ) + Y1,1 (q ,f )

(b) Show that F (q ,f ) is independent of θ and f .

(c) Why does this result show that the electron probability density for the
filled n = 2, l = 1 subshell is spherically symmetrical?