Problem Set 4

1. What is the distinction between a molecular solid and an ionic solid? Account for the
following observations:
(a) Solid PbBr2 does not conduct electricity, but when molten the salt is a good conductor.
(b) Neither solid naphthalene nor molten naphthalene conduct electricity.

(c) Metallic gold, both when solid and molten, conducts electricity.

2. What types of intermolecular forces are present in the following molecules: (a) butane
C4H10; (b) CH3F; (c) CH3OH; (d) CF4?

3. In the gas phase, ethanoic acid is thought to exist as a dimer, held together by two
hydrogen bonds. Suggest a structure for the dimer.
In the solid, oxalic acid, (COOH)2, forms extended chains, also held together by hydrogen
bonds. Sketch a likely structure for such a chain.

4. How does orbitals for H-atom and that for multi-electron atom differ in terms of the radial
and angular plots?

5. Calculate the effective nuclear charges (Zeff) of the following orbitals for Al and Ar.

6. The RDF for a 1s orbital is 4πr2[ 1s(r)]2.

Given that the 1s wavefunction is ψ1s(r) = 4N1s2 πr2 exp (-r/a0), show that the RDF is given by

(N1s is the pre-exponential constant in the 1s wave function)

We can find the maximum in this RDF by differentiating it with respect to r, and then setting
the derivative to zero. Show that the required derivative is

Further show that this differential goes to zero at r = a0, and use a graphical argument to
explain why this must correspond to a maximum.
For a hydrogen-like atom with nuclear charge Z, the 1s wavefunction is ψ1s(r) = N1s exp (-
Zr/a0). Show that the corresponding RDF has a maximum at r = a0/Z.

7. The contour plot shown below is of one of the 4p orbitals: positive intensity is indicated by
red contours, negative by blue, and the zero contour is indicated in green.
Sketch how the wavefunction will vary along the dotted line a, and along the two circular
paths b and c (for the latter two, this means making a plot of the wavefunction as a function
of an angle which specifies how far we have moved around the circle).