8.

314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan

6.022 10 mol

(1) 1pt. each

From the possible statements in columns A select the best match for each phrase in
column B and put its letter in the adjacent blank space in Column A. (2pts each)
Column A
Column B
The standing-wave approach to explain
(a) Heisenberg uncertainty principle
quantization of energy ------ j
A description of the quantum properties of matter
(b) An eigenfunction equation
in terms of wave functions ----.a
For operator and function f(x), f(x) = af(x)
(c)Stern-Gerlach experiment
(where a is a constant) is an
example of -----If two Hermitian operators with non-degenerate
eigenvalues commute-------The quantum mechanical phenomenon that a
particle can have a finite probability of being in a
region that it does not have sufficient energy to
penetrate (like, for example, for a quantum
mechanical oscillator) ------- o
The observation that quantum mechanics
approaches classical mechanics in the limit of
large quantum numbers p
A description of the quantum properties of matter
in terms of wave functions -----For operator and function f(x), f(x) = af(x)
(where a is a constant) is an example of ----The Hamiltonian operator for the hydrogen
molecule ion ( H2+)..r

(d)
(e) The virial theorem

(f) the concentration of a single reactant is changed

while holding all the other concentrations constant

(g) The wave function must vanish at the walls.

(h) A series of elementary steps

(i)
The boundary conditions imposed on the
wavefunction of the particle in the box that lead to
quantization.
In the method on initial rates-----

(j) de Broglies explanation

(k) every eigenfunction of one operator must be an
eigenfunction of the other operator.

Blackbody radiation---------------- n

(l)was suggested by Erwin Schrdinger

Wave particle duality-------------h

(m)normalization equation

Heisenbergs uncertainty principle.-------

(n)Emission spectrum by a body that is in

equilibrium with a radiation field specified by a
temperature T

d 1 ..

(o)Tunneling

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
6.022 10 mol

10 m/s (Spring 2016)

Name:Breyonna Morgan
For a molecule that is not subject to an external
potential, the total potential energy is equal to
the negative of twice the kinetic energy. The
proof of this statement is known
as. e
A harmonic oscillator (reduced mass and force
constant of 1 a.u
A rigid rotator wave equation..

(p) is called Bohrs correspondence principle

(q) px
(r)

2 2
e2
1
2m
4 0

1 1
e2
1

4 0 Rnuclei
r1 r2

(2) (1pt)Which of the following phenomena could be explained by classical physics and did not
require a quantum hypothesis in order to make theory agree with experiment?
(a) Blackbody spectra
(b) Diffraction of light
(c) Low-temperature heat capacity in perfect crystals
(d) The photoelectric effect
(e) Orbital motion of planets
(f) (b) and (e)
(g) (a), (b), and (d)
(h) None of the above
(3)

(1pt)Which of the following statements about the integral

Hermitian operator are true?

(a) It must be zero if g is an arbitrary eigenfunction of

(b) It must be a real number
(d) It is equal to zero if A has even parity
(f) (a) and (b)
(h) None of the above

g | A| g

where

is a

A(c) It is equal to A< g | g >

(e) It is zero if [H,A] = 0
(g) (a) and (c)

(4) (1pt)
Which of the following statements about the de Broglie wavelength are true?
(a)decreases as mass increases if velocity is constant
(b) =h/p
(c) decreases as momentum increases
(d) increases as kinetic energy decreases
(e) A particle that has zero velocity has an infinite de Broglie wavelength
(f) All of the above
(g) (a), (b) and (e)
(h) (c) and (d)
(5)
(1pt)Which of the following is (or are) the time-dependent Schrdinger equation in one
dimension?

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan
(a)

2 x, t 2 2

V x x, t
2
2
i
t
2m x

(b)

x, t
2

V x x, t
i
t
2m x

(c)

(e)

x, t 2 2

x, t
2
i
t
2m x

1 2 x, t
c2

t 2

2
x 2

x, t

6.022 10 mol

(d)

2 x, t 2 2

x, t
2
i
t 2
2m x

(f) H x, t T V x, t

x, t 2 2

V x x, t This should have been the answer. See equation 13-27
2
i
t
2m x

lectures. Suean gets credit for this.

Fill in the blanks (Show your work)
(6) (2pt)A 100 W sodium-vapor lamp emits yellow light of wavelength of 550 nm.
(i)The frequency of the radiation is --------------------------- (show your work)

(ii) (2pt)The wavenumber of the radiation is..

(iii)The number of photons emitted per second equals..

(7)(i) (1pt)To be physically acceptable, a quantum-mechanical wavefunction must be

------------------

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
6.022 10 mol

10 m/s (Spring 2016)

Name:Breyonna Morgan

(ii) (1pt)Consider a quantum-mechanical eigenvalue equation

be------------ and the eigenvalue, a n must be.

An ann

, the operator

must

(iii) (1pt)The physical significance of the eigenvalue a n is --------------------Show your work in differentiation and integration

(8)

(i) (2pt)Which of the following is an eigenfunction of the operator

(a) eikr

(b) sin(kr)

(c)

e ikr
r

(d) re ikr

(e)

pr r r r

e kr

(ii) (1pt) what is the corresponding eigenvalue in (i)

k
(9) 1pt Spherical polar coordinates are used in the solution of the hydrogen atom Schrodinger
equation because
(A) the Laplacian operator has its simplest form in spherical polar coordinates.
(B) cartesian coordinates would give particle-in-a-box wavefunctions.
(C) the Schrodinger equation is then separable into 3 ordinary diffential equations.
(D) otherwise the atomic orbitals would violate the Pauli exclusion principle.
(E) Schrodinger first used this coordinate system; any other coordinate system would be equally
convenient
(10) Which of the following statements about tunneling are true?
(a) Tunneling is more efficient near the top of the barrier than further down
(b) Tunneling is responsible for the radioactive emission of -particles
(c) Tunneling is more efficient for lighter particles
(d) Tunneling has no classical analog
(e) Tunneling is more efficient the narrower the barrier
(f) (c) and (d)
(g) All of the above
(h) None of the above
(11) (4pt) Locate the radial nodes in the 3p orbital of an H atom where. The radial wavefunction is
given by 3 p

1 Z

4861 / 2 a

3/ 2

4 e / 2 where

2Z
r (See page 324 of Atkins)
na

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan

6.022 10 mol

(12) (4pt)The wavefunction for the 2p orbital of a hydrogen atom is Ne-/2, where is (2Z/na)r
Determine the normalization constant N.

(13) (4pt)What is the orbital angular momentum of an electron in the orbitals (a) 2s, (b) 4p, (c) 4d?
Give the numbers of angular and radial nodes in each case. (See pages 223-224)

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
6.022 10 mol

10 m/s (Spring 2016)

Name:Breyonna Morgan

(14) (2pt) What are the allowed total angular momentum quantum numbers of a composite system in
which j1 = 2 and j2 = 1?

(15)3pts Give the ground-state electron configurations of (a) CN, (b) NO +, and (c) OF+. See pages
(217 word pro chapter 19)

(16) (2pt) An Operator

is such that H

H
H1234
1

2 1 , H 2 2 4 2 , H 3 3 1 3 ,

and H 4 4 6 4 . If 1 , 2 , 3 , and 4 are normalized, what is

a l space 1 2 3 4 H 1 2 3 4 d

is

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
6.022 10 mol

10 m/s (Spring 2016)

Name:Breyonna Morgan
(a) 3
(b) 42

(c) 11

(d) 13

(e) 15

( See page page 188 wordpro 15)

For the next three questions, consider a Hckel theory calculation on planar
neutral 1,3,5hexatriene with carbon atoms numbered as indicated. See pages 228-230)
2
1

4
3

(17) (2pt)Which of the following statements is/are not true about Hckel theory
in general?
(a) The Hckel theory many-electron wave function is the Hartree product of
the molecular orbitals
(b) Hckel theory is an iterative self consistent field procedure
(c) The basis set is one p orbital per carbon atom, with all p-orbitals parallel
(d) All resonance integrals in the secular determinant are replaced by either
zero or empirically
determined values
(e) The final MOs are expressed as a linear combination of AOs
(18) (2pt) Which of the following statements is/are not true about a Hckel
theory calculation for 1,3,5-hexatriene?
(a) There are four occupied MOs in the final wavefunction
(b) H 23 H 56
(c) The terms in the secular determinant have dimension 6 x 6 matrix
(d) H 14 S14
( See page page 222-229, wordpro 20)
(19) (1pt)If is a guess wave function, H is the Hamiltonian, and E0 is the ground-state energy,
which of the following is/are always true as a consequence of the variational principle?

Hdr
*
dr
*

(a) * Hdr

E0

(b)

Hdr
*
dr
*

E0

(c)

E0

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

6.022 10 mol

10 m/s (Spring 2016)

Name:Breyonna Morgan
(d)The expectation value of H over will be less than E0
(e) The expectation value of H over will be greater than E0 + 1/2 a.u.

(20) (1pt)What is the Born-Oppenheimer approximation?

(a) Assuming nuclear and electronic motions to be decoupled so that electronic energies can be
computed for fixed nuclear positions
(b) Assuming identical quantum mechanical particles to be indistinguishable from one another
(c) Ignoring spin-orbit coupling in the Hamiltonian
(d) Assuming that spin can be included in an ad hoc fashion
(e) Leaving zero-point vibrational energy out of the potential energy surface
(f) Mistaking Max Born for Robert Oppenheimer
(g) Assuming electrons to be lighter than nuclei
(h) All of the above
( See page page 210 wordpro 19)
(21) (1pt)Which of the following statements about the secular determinant is/are true? See pages
228-230)
(a) The secular determinant is N x N where N is the number of basis functions
(e) In each element, H ij S ij
(b) Each element of the secular determinant involves a resonance integral, an overlap integral,
and a molecular orbital energy
(f) In the absence of degeneracy, there will be N values of Ej each one of which will have
associated with it basis set coefficients aij for an associated molecular orbital.
(c) It must be set equal to one in order to find molecular orbital coefficients
(g) (a), (b), (e), and (f)
(d) In each element, Hij > Sij (h) All of the above
(22) (2pt)Use Hunds rule to deduce the lowest spectroscopic energy state of an excited state of
berrylium atom whose electron configuration is (1s2)2s13s1 (See pages 223-224)

(23) (3pt)Deduce the value of J associated with the term symbols 4F, 2S, 3D(See pages 223-224)
For 4F
2S + 1 = 4
S = 3/2
L=4
L + S = 4 + (3/2) = 11/2
L - S = 4 - (3/2) = 5/2
So, J = 5/2.......11/2
For 2S
2S + 1 = 2

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan
S = 1/2
L=0
L + S = 0 + (1/2) = 1/2
L - S = 0 - (1/2) = -1/2
So, J = -1/2.......1/2

6.022 10 mol

For 3D
2S + 1 = 3
S=1
L=2
L+S=2+1=3
L-S=2-1=1
So, J = 1.......3

(24)Calculate the frequencies in the lines in the 3d 2D to 2p 2P1,2 for atomic hydrogen

(25) (3pt)For the ground state of the helium atom, the Slater determinant for the approximate
wavefunction can be written, in abbreviated notation, as follows: (See pages 221-222 of lecture
notes)

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan

6.022 10 mol

1 1s1 1s 1
1,2
2 1s2 1s 2

Write a similar expression from the Lithium atom

(26) (2pt)The lowest excited state of the helium atom has the term symbol (See pages 223-226)
1
(a) 2s1 (b) 3S1
(c) 3S0
(d) 1+g
D2
(27) (2pt)Which of the following transitions are allowed in the normal electronic emission
spectrum of an atom: (a) 3s 2s, (b) 3p 2s, (c) 3d 3p?
(28) (2pt)In atomic units, what is the Hamiltonian for the Be atom?
(a)

2 i 4 2 1 i4 Ze2 1 i4, j 4 e2
H i

2me i1
4 0 i1 ri 4 0 i1, j 1,i j rij

(b)

2 i4 2 1 i4 4e 2 1 i4, j 4 e 2
H i

2me i1
4 0 i1 ri 4 0 i1, j 1,i j rij

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan
(c)

2 i 6 2 1 i 6 6e 2 1 i 6 , j 6 e 2
H i

2me i1
4 0 i1 ri 4 0 i1, j 1,i j rij

(d)

2 i2 2 1 i2 Ze 2 1 i2, j2 e 2
H i

2me i1
4 0 i1 ri 4 0 i1, j 1,i j rij

6.022 10 mol

(29) (2pt)

A Huckel molecular-orbital computation on fulvene

shown to the right gives the following secular determinant where
x

.Choose the correct answer,

2
1

5
6

x 1 0 0 0 0 x 1 0 0 0 1 x 1 0 0 1 0
1 x 1 0 0 0 1 x 1 0 0 0 1 x 1 0 0 1

0 1 x 1 0 0 0 1 x 1 0 0 0 1 x 1 0 0
(a)
(b)
(c )

0
0
1
x
1
0
0
0
1
x
1
0
0
0
1
x
1
0

0 0 0 1 x 1 0 0 0 1 x 1 1 0 0 1 x 1

0
0
0
0
1
x
1
0
0
0
1
x
0
1
0
0
1
x

x 1 0 0 1 0
1 x10 01

0 1 x 1 0 0

x 10 010
1 x10 0 0

01 x10 0

(d )

(e)

0 0 1 x 1 0
10 01 x 1
0 1 0 0 1 x

answer is e

0 01 x10
10 01 x1
0 0 0 0 1 x

8.314 J
mol K , c=3.0 x
Physical Chemistry Exam 3, Spring 2010. h=6.626 x 10-34J.s, k= R
23
N

10 m/s (Spring 2016)

Name:Breyonna Morgan

6.022 10 mol

(30) 2pts. The illustrated wavefunction represents the state of the linear
harmonic oscillator with
1/ 4

Given that o

x 2
2

4 2 mk

where
h 2

1/ 2

is the ground state harmonic oscillator

V (r ) where V (r ) 12 kx
The expression that can be used to evaluate V (r ) is
2

wavefunction, evaluate

1
(a) V ( r ) kx 2

2

V ( r )

(c) V (r ) 0

x 2
2

1/ 4

x 2
2

x 2
2

(b)

dx

1 2
kx
2

1 2
kx

V (r )

1/ 4

1/ 4

1/ 4

x
2

1/ 4

x 2
2

dx

(d)

dx

1 2
kx
2

1/ 4

x 2
2

dx