University of Pennsylvania

Department of Chemistry
Chemistry 221
Mid-Term Examination 1
Wednesday, Oct. 4, 2006
Since time is limited, use labeled diagrams and/or equations to illustrate your answers. TA's will be
looking for appropriate explanation and justification.
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1. (a) (9 pts) Explain with the aid of diagrams what is meant by the following terms:
(i) Black body radiation,

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(ii) Stefan-Boltzmann Law,

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(iii) Ultraviolet catastrophe.

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(b) (8) You are told that the wavelength of the n=3 → n=2 fluorescent transition of the hydrogen

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atom lies at 656 nm (Balmer Series). Calculate the wavelength corresponding to the (high-energy)
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convergence point of this series.
(c) (8) Suppose that light from an excimer laser at a wavelength 254 nm were incident on a metal
surface having a work function of 2.0 eV. Calculate the maximum possible velocity (in m s-1) at
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which electrons could be ejected from the surface by the photoelectric effect.
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2. (a) (9) Write down in each case a simple quantum mechanical equation that explains what is
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meant by the terms:

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(i) probability density, (ii) average value, (iii) orthonormality.

(b) (8) Explain what is meant by the following terms:
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(i) variance
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(ii) quantum number

and explain how these may relate to the Heisenberg Uncertainty principle.
(c) (8) In Chapter 4, the book mentions a number of quantum mechanical postulates. State two of
them in your own words, with a brief explanation and/or illustration.

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 3. (a) (9) The function ψn(x):

2  nπ x 
ψ n ( x) = sin  
a  a 

Is an eigenfunction of one of the following operators:

ℏ d ℏ2 d 2 ℏ ∂ ∂ 
; − + V ( x) ;  y −z 
i dx 2m dx 2 i  ∂z ∂y 
(i) Pick the correct operator and justify your choice.
(ii) What eigenvalue(s) would you generate by applying the operator you choose to the
given wavefunction?
(iii) To what properties do the other two operators relate? Use a diagram or a mathematical

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expression in each answer.

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(b) (8) Explain what is meant by the term “degeneracy”. Give examples of two distinct types of

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quantum mechanical system that exhibit this behavior.
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(c) (8) Briefly explain the two following concepts, with the aid of diagrams:
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(i) Classical turning point, as related to the quantum mechanical harmonic oscillator,
(ii) Quantum mechanical tunneling.
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4. (a) (6) Explain some similarities and differences between the eigenfunctions of the Hamiltonian
for a hydrogen atom and a diatomic molecule.
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(b) (5) Write down the general form of the Hamiltonian Operator for the 1-D Harmonic Oscillator.
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(c) (8) Draw one diagram for each case, describing the energy level structure for:
(i) A rigid rotor
(ii) A harmonic oscillator.
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Label each one in detail and point out the similarities and differences.
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(d) (6) With the aid of information at the end of the test, prove that the microwave transitions of a
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molecule acting as a rigid rotor will be separated by the quantity: Hz.
4π 2 I

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 Information
1 Debye (D) = 3.336 H 10-30 C m
Planck's Constant = 6.6262 H 10-34 Joule sec.
Boltzmann's Constant = 1.381 H 10-23 Joule K-1
Gas Constant = 0.08206 liter atmos mole-1 deg-1 = 8.314 Joule mole-1 deg-1
Velocity of Light in Vacuo = 2.9979 H 108 meter sec-1
Avogadro's Number = 6.022 H 1023 molecules mole-1
Charge of electron = 1.602 H 10-19 Coulomb
Mass of electron = 9.109 × 10-31 kg
1 eV / 8066 cm-1 / 96.485 kJ mole-1 ≡ 1239.5 nm

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1Å / 10-10 meter

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E= Hψ = Eψ
λ

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J ( J + 1)ℏ 2
EJ = = BJ ( J + 1)
2I 4
2π 5 k B 1 2 p2 n2h2
L = J ( J + 1) ℏ σ= = 56.7 nWm -2 K -4 Ek = mv =
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=
15c 2 h3 2 2m 8mL2
Lz = ml ℏ
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E ( x, t ) = E0 cos ( ωt − kx )
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