Microscopic Physical Chemistry ( CHEM 4420 )

Mid-term Exam 3 ( Wednesday, 30 April 2014 )

This is a closed-book, closed-notes exam administered in a 1-hour class period.

NAME: ___________________________

RIN Number: ___________________________

Write out all work and answers on these pages.

If extra sheets needed,

(1) use provided,
(2) refer to extra sheets on exam pages,
(3) save & staple to exam when turned in.

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Grading Area: FOR TA USE ONLY,

Problem graded score max value

1 14
2 12
3 4
4 12
5 22
6 4
7 6
total 74

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Useful physical constants.

symbol meaning value

h Planck’s const 6.626 × 10 34 J⋅s
−

ħ (h / 2π) 1.055 × 10 34 J/(rad/s)

−

c speed of light 2.998 × 108 m/s

kB Boltzmann’s const 1.38 × 10 23 J / K
−

= 0.695 cm 1 / K
−

NA Avogadro’s # 6.022 × 1023 molec / mole

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(1) [ 14 pts ] The ro-vib spectrum of HCl is depicted at
right. Provide a brief reason for each of the
following observations.
[ Hint: each has to do with the fact that
more than one isotope is common for
chlorine atoms. ]

(a) [ 3 pts ] Two sets of peaks appear at distinct

amplitudes. Explain the ratio of amplitudes for
the two sets.

35 37
The amplitude ratio is given by the natural isotopic abundance of Cl (~75%) and Cl (~25%). Thus, the
35
approx 3× higher peaks correspond to Cl. The Q branch has ΔJ = 0 and Δn = 1.

(b) [ 3 pts ] One set is uniformly shifted in frequency

from the other. Explain what is responsible for the
shift.

The frequency shift is due to the fact that EJ = hcB(J(J+1)), where B ∝ (1/I = 1/µr02).
For spectroscopy, the more exact reason is that the energy spacings are in multiples of hcB,
2 37
and thus also ∝ (1/µr0 ). Because Cl has the larger reduced mass, it has smaller energy
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spacings Cl.

(c) [ 3 pts ] On the plot above, clearly label the regions that correspond to the P, Q and R
branches
(solution provided on plot).

(d) [ 3 pts ] What values of ΔJ and Δn correspond to the Q branch?

Solution: The Q branch has ΔJ = 0 and Δn = 1.

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(e) [ 2 pts ] Is the above spectrum consistent with a diatomic molecule?
Explain your answer in terms of the selection rules for diatomics.

Solution: Yes. The Q branch is absent because diatomics have the selection rule ΔJ = ±1.
Therefore, ΔJ = 0 (the Q-band location) is disallowed. Features that are present correspond to
transitions with ΔJ = −1 (P) and ΔJ = +1 (R).

(2) [ 12 pts ] Slater determinants are used to set up n-electron

wavefunctions [ Ψ(1,2, …n) ] in the orbital approximation. The
determinant guarantees that the resulting product state will be
physically acceptable.
a. [ 4 pts ] Name two distinct properties of the wavefunction that
are guaranteed by using a Slater determinant?

Solution: (1) Indistinguishability of the electrons (i.e., the wavefunction is

antisymmetric)
(2) Satisfaction of the Pauli exclusion principle.

b. [ 2 pts ] What is the electronic configuration for the ground

+
state of C ?
+ 2 2 1
Solution: C is a five-electron system, and its configuration is 1s 2s 2px

c. [ 6 pts ] Write the Slater determinant for Ψ(1,2,…n)

+
representing the ground state of C . Use the orbital notation
described in lecture notes,
i.e., from lecture, where I defined φ(electron #)
orbital type, spin state
, for
example φ(3)
3d,α
would correspond to the electron
labeled “3” residing in a 3d orbital with spin state
α (spin up).
Do not evaluate the determinant.

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 Solution: The five-electron system will fill the states
!1s," , !1s,# , ! 2s," ,! 2s,#and! 2px," and the Slater determinant sets up an anti-
symmetric wavefunction with indistinguishable representations of the five
electrons.
(1) (1)
"1s,! "1s,! "(1)
2s,!
"(1)
2s,!
"(1)
2px,!
(2) (2)
"1s,! "1s,! "(2)
2s,!
"(2)
2s,!
"(2)
2px,!
1 (3) (3)
!(1,2,3,4,5) = "1s,! "1s,! "(3)
2s,!
"(3)
2s,!
"(3)
2px,!
5! (4) (4)
"1s,! "1s,! "(4)
2s,!
"(4)
2s,!
"(4)
2px,!
(5) (5)
"1s,! "1s,! "(5)
2s,!
"(5)
2s,!
"(5)
2px,!

Evaluating this determinant gives the final form of the wavefunction, and it is
easy to verify that it is antisymmetric.

(3) [ 4 pts ]The Hamiltonian for a one-dimensional harmonic oscillator

ħ! ! ! !
is ! =   −
!! !" !
+ ! !!! ! ! . By using the trial function,
!!! !
!=! , we are able to use the Variational Method to get
!
!!
! ∗ !" ħ! ! !!!
!! = ! = +
!∗! 2! 8!
!!
Find the value of α which optimizes the trial function.

ħ! !
d!! /dα = 0 =
!!
− ! !!! /!!

Therefore, α = !!/2ħ

(4) [ 12 pts ] Given are the plots that correspond to 1s states of row
two elements with (Z−ζ) vs Z, and (Z−ζ)/Z vs Z. The plots
incorporate ζ1s for row 2 elements in their neutral state, as
reported in Table 21.1 of Engel & Reid.
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a. [ 4 pts ] Provide a physical explanation for the observed trend
of increasing (Z−ζ) with Z.

Solution: As Z increases across row 2, additional electrons are added in the

n = 2 level. As more electrons are added the magnitude of the shielding,
characterized by (Z−ζ), increases.
Incidentally, if we utilize language of the orbital approximation, these first fill
st th
in the 2s states and then the 2p states. It is interesting that the 1 and 4
additions to p-type orbitals have no apparent effect on ζ1s. However, I
haven’t an immediate explanation for these plateaus, and note that they do
not occur in plots of (Z−ζ2s).

b. [ 4 pts ] Based on this, do you expect the 2s orbitals for atoms

across row 2 to be the same or distinct in the Hartree-Fock
limit?
Solution: The 2s orbitals will be distinct from one atom to the next.
These orbitals are HF-SCF solutions to one-electron Schrödinger
equations, and they change (due to changing Veff) when electrons
are added (and when Z is increased).

c. [ 4pts ] Provide a physical explanation for the observed trend

of decreasing (Z−ζ)/Z.

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 Solution: This plot shows the fractional screening, (Z−ζ)/Z, of the nuclear
charge. As we go across the row 2 elements, we add one proton and one
electron in each step. Each successive electron is a bit less effective at
screening its “accompanying” proton than was the previous one because it
moves into higher orbital types with P(r) extending further from the nucleus.
Thus, the fractional screening actually decreases.

(5) [ 22 pts ] The following Hamiltonian corresponds to the atomic

electronic system at right.

" !! 2 % 2
Ĥ = $$ ( 2
'' (e1+ (e2 ) (i)
# 2me &
⎛ Ze2 ⎞ ⎛ 1 1 ⎞
− ⎜ ⎟ ⎜ + ⎟ (ii)
⎝ 4πε0 ⎠ ⎝ r1 r2 ⎠
⎛ e2 ⎞ ⎛ 1 ⎞
+ ⎜ ⎟ ⎜ ⎟ (iii)
⎝ 4πε0 ⎠ ⎝ r12 ⎠

(a) [ 6 pts ] Sets of terms from Ĥ above are labeled (i), (ii), and (iii). Briefly define the energy
contribution represented by each term.

(i)
Kinetic energy of the electrons

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 (ii)
Coulombic attraction potential between the electrons and the nucleus

(iii)
Repulsive Coulombic potential between the electrons

(b) [ 5 pts ] Write the Hamiltonian for the H2 molecule shown on

the right.

[ 3 pts ] Which term or set of terms renders it impossible to

analytically solve the corresponding Schrödinger equation?

The repulsive Coulombic potential energy between electrons 1

and 2.

(c) [ 4 pts ] For the diatomic system above the terms for the
Hamiltonian that relate only to nuclear coordinates. [ Label
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 these terms for reference in part (e). ]

" !! 2 %
Solution: Terms for nuclear KE: (iv) → $$
# 2mp &
' (
' ( 2A + (B2 )
# e 2Z Z & # 1 &
and Coulombic nuc-nuc repulsion: (v) → %% A B(
(% R (
$ 4!" 0 '$ '

(d) [ 4 pts ] What is the effect of the Born-Oppenheimer approximation on each of the terms in
(d)? [ Be clear by referring to your labels in (d).]

Solution: With B.O., we assume nuclei are fixed (i.e., no motion, constant R). So, term (iv) vanishes,
and is used only in the vibrational Sch.Eqn, which is treated as a separate problem.
Additionally, term (v) becomes a constant, allowing independent solution of the
electronic problem at a given R. Repetition vs. R specifies the vibrational potential.

(6) [ 4 pts ] Why does the effective nuclear charge for the 1s orbital increase by 0.99 in going from
oxygen to fluorine but only increases by 0.65 for the 2p orbital?

Because the radial probability distribution of the 1s electron is quite localized, there is no orbital space
between the 1s and the nucleus and since there are no electrons that are added to the 1s level in
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going from oxygen to fluorine, the 1s electron feels the full increase in the nuclear charge in going
from oxygen to fluorine. By contrast, the 2p electrons are more delocalized. As an additional p
electron is added in going from oxygen to fluorine, only a part of the increase in the nuclear charge is
negated by shielding due to the additional 2p electron. Adding an electron in the same shell is not as
effective in shielding as adding an electron in an inner shell.

(7) [ 6 pts ] The neutral configuration of Lithium (Li0) is 1s22s1 with nuclear
charge Z = 3, whereas Beryllium has the configuration 1s22s2 and Z = 4.
The plot at right shows realistic representations of 1s & 2s radial
distribution functions. These are qualitatively correct for both Li0 and
Be0, and may be conceptually useful in considering your answers here.

(a) [ 2 pts ] How many electrons contribute to screening a 2s electron in Be0? ____________

3 (2 from 1s-type orbitals plus 1 from the 2s)

(b) [ 2 pts ] The total screening experienced by a 2s electron in a given atom is (Z−ζ2s). In
comparing this value for Be0 and Li0, circle which of the following is correct.

(i) ( Z − ζ 2 s ) Be0 < ( Z − ζ 2 s ) Li0

(ii) ( Z − ζ 2 s ) Be0 = ( Z − ζ 2 s ) Li0

(iii) ( Z − ζ 2 s ) Be0 > ( Z − ζ 2 s ) Li0

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(c) [ 2 pts ] Consider instead the value ξ2s ≡ (Z−ζ2s)/Z, which is a marker of the effectiveness of
screening in a 2s orbital. Circle which of the following is correct.

(i) (ξ 2 s ) Be0 < (ξ 2 s ) Li0

(ii) (ξ 2 s ) Be0 = (ξ 2 s ) Li0

(iii) (ξ 2 s ) Be0 > (ξ 2 s ) Li0

Explanations:
(a) A 2s electron is strongly screened (~<1 charge unit contributed to screening) by each 1s
electron since the latter reside almost completely between the 2s and the nucleus.
Additionally, each 2s electron in Be0 will screen the other, but only weakly, contributing
<<1 charge unit to screening because it spends so little fractional time within the other
2s. Thus, the 2s experiences total screening ~<2 charge units, meaning (Z − ζ2s) >~2
so 1.5 < ζ1s < 2.5
The actual value is ζ2s = 1.91.
(b) As more electrons are added, there is always more screening. This explains why
total screening is bigger for Be0.
(c) However, each added electron is less effective than the previous. So as you go
across the periodic table, each step increases Z by 1, but increases screening by a bit
less than 1. Thus, screening efficacy is less for Be0.

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BLANK PAGE PROVIDED AS EXTRA WORKSPACE.

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BLANK PAGE PROVIDED AS EXTRA WORKSPACE.

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