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CHM 217

Final Examination

1. Solve the one-particle three-dimensional time-independent Schrodinger equation for the


free particle.

2. Show that 0(x) = (x02)-1/4 exp [-1/2(x/x0)2]; E0 = 1/2h satisfies Schrodinger’s equation
– ħ2/2m d2/dx2 + 1/2kx2 = E for the linear, harmonic oscillator.

3. For the ground state of the one-dimensional harmonic oscillator, find the average value of
the kinetic energy and of the potential energy. Verify that <KE> = <PE>

4. A lithium atom, mass 1.17 x 10-26 kg, is vibrating with simple harmonic motion in a
crystal lattice, where the force constant k is 64.0 N/m.
a. What is the ground state energy of this system in eV?
b. What would be the wavelength of the photon that could excite this system to
the n = 1 level?

5. The atoms in a nickel crystal vibrate as harmonic oscillators with an angular frequency of
2.3 x 1013 rad/s. The mass of a nickel atom is 9.75 x 10-26 kg.
a. The effective interatomic force constant for nickel is __________.
b. The spacing of the vibrational energy levels of nickel is _________.

6. The lowest energy level of a certain quantum harmonic oscillator is 5.00 eV. The energy
of the next higher level is closest to ________.

7. For the one dimensional harmonic oscillator in the ground state, calculate the expectation
<x> of x and the expectation <x2> of x2. The statistical standard deviation

x = (<x2> - <x>2)1/2
is a measure of the experimental uncertainty in any measurement of the position of the
particle. Similarly, the quantity calculated from

p = (<p2> - <p>2)1/2
is a measure of the experimental uncertainty in any determination of the momentum of
the particle.

Calculate the product x p and show that it is of the order of magnitude of ħ. The
result is a special case of the Heisenberg Uncertainty Principle.
8. Estimate the value for Erot for the lowest rotational energy state of N2, which has a bond
length of 0.110 nm.

9. Huckel molecular orbital theory may be applied to conjugated structures containing a


heteroatom. Thus formaldehyde H2C=O has a Huckel diagram analogous to ethylene
except that the Huckel parameter  which is the (negative) energy of a valence electron
in an isolated carbon atom must be lower than  for an isolated, more electronegative
oxygen atom, and empirically choose this lower energy to be  + . Thus, the diagonal
element H22 of the Hamiltonian matrix H is H22 =  + . The remaining matrix elements
are unchanged.

1 2
Carbon Oxygen

a) Calculate the energy levels, ground state molecular energy, and Huckel molecular
orbitals for formaldehyde.
b) By comparing the total molecular energy with the energy of an electron in an isolated
carbon atom plus the energy of another electron in an isolated oxygen atom, calculate
the bond energy of the molecule in the ground state.
c) Compute the electron density on the carbon and the oxygen atoms. The dipole
moment of a molecule is a vector pointing from the negative toward the positive
center of charge. What is the direction of the dipole moment of formaldehyde?

10. You are given the following energies and MO expressions for butadiene.

X = -1.618  = 0.37171 + 0.60142 + 0.60143 + 0.37174

X = -0.618  = 0.60141 + 0.37172 - 0.37173 - 0.60144

X = +0.618  = 0.60141 - 0.37172 - 0.37173 + 0.60144

X = +1.618  = 0.37171 - 0.60142 + 0.60143 - 0.37174

Use this information to calculate the molecular orbital energy levels of the
cyclobutadiene. Compare this with the energies obtained by exact Huckel solution of
the cyclobutadience problem.
d)