CHEM2420 Physical Chemistry II

Problem Set 1
Feb. 5, 2016
Due on Feb. 19, 2016

Time-independent Schrdinger Equation

104
2 ( x )
V ( x ) ( x) E ( x)
2m x 2
2

Constants
0 8.8542 1012 C2 N 1m 2

h 6.626 1034 J s
me 9.109 1031 kg
amu 1.661 1027 kg
e 1.602 1019 C
c 3.0 108 ms 1
1. Explain that the wave nature of a macroscopic matter does not affect any
properties, but it is very important in atomic scale based on the calculation of the
wave length of matter wave of (a) a ball with mass 300 g traveling at a speed of 20
m/s, and (b) an electron traveling at 8x107 m/s.
2. The Heisenberg uncertainty principle is important in quantum mechanics.
(a) State the equation of the Heisenberg uncertainty principle The Heisenberg
uncertainty principle.
(b) What is x for an electron with v = 0.03 m/s.
(c) What is x for a ball, whose mass is 0.20 kg, with v = 0.250 m/s.
3. Use the idea of Bohr model of hydrogen atom to derive the Rydberg constant, RH,
in the units of joule (J) and wave number (cm-1). Hints:
(a) The sum of electrostatic force and centrifugal force equal to zero.
(b) The total energy is the sum of kinetic and potential energies.
(c) The quantization assumption made by Bohr.
1
1
(d) The Rydberg equation for hydrogen spectrum is RH 2 2 .
n1 n2
4. The core of quantum chemistry is to solve the time-independent Schrdinger
Equation (TISE). The 1 dimensional particle in a box (1D PIAB) is the easiest
problem for TISE.
(a) The solution, wave function, contains all information of the system. What are
the three boundary conditions for the wave function?
(b) Suppose that a 1D PIAB is built in the z direction with the length b and the
mass of the particle is m. First draw the box. Then solve the TISE for this box.
Note that the equation to be solved is a simple second-order differential
equation.

5. Use bond energies to estimate H for the oxidation of methyl hydrazine by

dinitrogen teroxide.

12H2O(g)+9N2(g)+4CO2(g)
6. Use propionic acid as an example to show how you would analyze the NMR
spectra; in other word, try to sketch the NMR spectra of propionic acid.

7. The energy levels of heteronuclear diatomic molecule is

h2
EJ 2 J ( J 1) hBJ ( J 1)
8 I
and the transition for rotational spectra is from J to J+1
(a) Derive the energy E of the rotational transition.
(b) Sketch the first six lines of a rotational spectrum clearly indicate J and the
spacing between lines.
(c) Calculate the reduced mass of 1H35Cl. The mass of 1H is 1.0078 amu and the
mass of 35Cl is 34.9689 amu.
(d) Calculate the moment inertia I of 1H35Cl.
(e) The wavelength of microwave spectrum of 1H35Cl shows the transition from J
= 3 to J = 4 is 1.212 104 m. Calculate the bond length of the 1H35Cl molecule.
8. For a conjugated double bond molecule 1,3,5-hexatriene (C6H8),
(a) What is a good model for the electrons?
(b) Calculate the energy levels of this model. Assume the molecule is linear with
bond lengths 135 pm for C=C and 154 pm for C-C.
(c) Fill all electrons in the MO built form the model in to obtain the ground state
electron configuration of electrons.
(d) What are the quantum numbers for HOMO and LUMO, respectively?
(e) What is the energy required to excite an electron from the ground state to the
first excited state?
(f) What is the region of electromagnetic radiation? Note, uv, visible, IR,...etc.
9. Draw structures of each of the following.
(a) trans-diqauabis(ethylenediamine)copper(II) ion.
(b) SF4. Is it polar or nonpolar?
10. Sketch and explain the most likely crystal field diagram for the
( tran[Ni(CN)4(NH3)2]2+ complex ion. Assume the NH3 ligands lie on the z axis.
11. For the three species CO, CO+, and CO2+,

(a) Using the molecular orbital model to describe the bonding predict the bond
orders and the relative bond lengths for these three molecules.
(b) How many unpaired electrons are present in each species.

12. For the molecule biacetyl, CH3COCOCH3

(a) Write the Lewis structure by showing all lone pairs.
(b) What is the formal charge of each C and O?
(c) Predict values for all C-C-O and C-C-C bond angles.
(d) How many bonds?
(e) How many bonds?
(f) Give the hybridization of all carbon atoms in the bonding.
(g) Must the four carbons and two oxygens lie in the same plane? Explain.
(h) Is biacetyl polar or nonpolar?
13. The hydrogen-like atomic orbitals are used for all atoms and the electrons are
filled in atomic orbitals according to the Aufbau principle.
(a) State the Aufbau principle.
(b) What is the atom with the electron configuration, [Ar]3d44s14p1, and its
atomic number Z?
(c) What is the ground state electron configuration of the atom in (b)?
(d) Order the ionization energy of atoms with atomic number Z-1, Z (as in (b)),
and Z+1.
14. This problem is about the homonuclear diatomic molecules composed of atoms of
the second period.
(a) What is the principle quantum number of valence orbitals of these atoms?
(b) What are the atomic valence orbitals and their quantum numbers (n, l)? List all
of them.
(c) Sketch the molecular orbitals and label label their types (or ; bonding or
antibonding) that would be formed with the valence orbitals. There are eight
molecular orbitals formed by these atomic valence orbitals.
(d) Order the eight MOs according to their energies.
(e) Use the Aufbau principle to determine the electron configuration of B2. What
is the bond order?
(f) Use the Aufbau principle to determine the electron configuration of C2. What
is the bond order?