February 17, 2018 CYL 100

Practice Problem Set 3

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1) True or False? (a) In the electronic Schrödinger equation, VNN is zero, (b) in the electronic
Schrödinger equation, VNN is a constant, (c) there is no internuclear repulsion in the H2+, (d) the
molecular wave function of H2 is experimentally observable, (e) the ground electronic state of
H2+ is a bound state, f) the entropy change is positive when O2 binds with the Fe center in the
enzyme hemoglobin in our body, g) according to Born-Oppenheimer approximation, the
complete molecular wave function Ψ can be written as Ψ = Ψe × ΨN , where Ψe and ΨN are
electronic and nuclear wave functions, respectively, h) the entropy change is negative for
cooling of a cup of hot coffee to room temperature, i) a delta bond is stronger than a π bond., j)
the electronic energy depends on the internuclear distance, k) the molecular electron
probability density is experimentally observable, l) the lowest energy MO for benzene system
has two nodes, m) in the electronic Schrödinger equation, VeN is zero.

2) Draw the antibonding interaction when two dx2-y2 orbitals overlap in a delta fashion.

3) Look at the following molecule called cyclobutadiene

a) Draw all the π-MOs, b) write down the LCAOs for each of the π-MO, c) Identify the LUMO, d) what is
the spin multiplicity of this system?

(Hint: The π-MO2 will have one node through the opposite bonds and π-MO3 will have one node through
the opposite atoms)

4) What type of bond is formed when a dxy orbital overlaps with a px orbital?

5) Write down the electronic Hamiltonian for H3+ system.

6) a) Write down the molecular electronic configurations for the species F2, F23+, F21–

b) Arrange those species in decreasing order of bond strength.

7) Find ΔS when 24 mg of a perfect gas N2 at 89 torr and 22°C expands adiabatically into
vacuum to a final pressure of 34 torr.

8) Find the hybridization of Xe atom in XeF2.

February 17, 2018 CYL 100

9) Consider the following three systems:

a) Which system has the lowest value for its translational entropy? b) Which system has the
largest value for its total entropy? c) Identify the most probable system (state).