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Chemistry 3830 Answers to Assignment #3

1. Draw a qualitative correlation diagram between the MOs for the linear and cyclic polyhydrogen systems, H
3
up to H
6
. Use
the symmetry-adapted orbitals from resource section 5 of your textbook. For a qualitative study of the orbitals and
electron occupation of the linear and cyclic polyhydrogen systems, H
3
up to H
6
use HyperChem calculations at the AM1
level. Correlate your results for the two versions of each molecule. Predict what the charge of the most stable (most
strongly bonded) version of each structure is (consider only neutral, 1+ and 1 charges as possibilities; higher charges
would be unrealistic in the extreme!)

My answers all have used the model builder to create the molecules. A few cases can be minimized, but others cannot, so
to be consistent I have used all model-built structures, with single-point AM1 calculations corrected only for charge and
multiplicity. H
3
has an odd number of electrons, so it is most logical to consider both the monocation and the monoanion.
In the monocation, the lowest energy structure is clearly the cyclic form, since the a orbital is overall more bonding than
is the 1
g
orbital:
a'
-29.8 eV
-6.5 eV
e'
+4.5 eV
-8.4 eV
-27.0 eV
1
g
2
g
1
u
H
3
+
cyclic linear

In the monoanion, the situation is reversed, because occupancy of e is worse than the less antibonding 1
u
. The slight
loss in bond energy for 1
g
is compensated for by the bigger gains in the upper orbital; we would predict a linear structure
for the H
3

molecule. NOTE: the cyclic form must be specified as a triplet ground state to get this (correct) picture. The
singlet form is a higher-energy species.
a'
-7.7 eV
+10.3 eV
e'
+15.4 eV
+1.5 eV
-7.7 eV
1
g
2
g
1
u
H
3
-
cyclic linear

H
4
is even-electron. Hence, we need only consider one electron count for this system. However, note again that the cyclic
form must be specified as a triplet ground state because of the degeneracy of the e
u
orbitals. The energetic preference is
for the linear system, because of the great stabilization of the non-bonding e
u
orbital as it becomes 1
u
. The loss of
bonding in the a
1g
level on going to 1
g
is small compared to this big gain; the system is more stable as linear.
a
1g
-21.8 eV
-1.9 eV
e
u
+5.7 eV
-10.5 eV
-19.5 eV
1
g
2
u
1
u
H
4
cyclic linear
b
2g
+5.7 eV
+3.4 eV
2
g

2-10
The H
5
system is again an odd-electron system. I will only present the monocation (you should try both!); interestingly
both the cation and the anion are more stable as the linear form. The preference is again caused by the conversion of the
non-bonding (weakly anti-bonding) e
1
orbitals to bonding 1
u
.
a
1
'
-33.9 eV
-13.7 eV
e
1
'
+2.7 eV
-20.7 eV
-29.2 eV
1
g
2
u
1
u
H
5
+
cyclic
linear
+3.7 eV
3
g
-4.5 eV
e
2
'
+6.9 eV
2
g


H
6
is again even, so there is only one possibility to consider. Here the more stable form is the cyclic form.
a
1g
-25.6 eV
-10.0 eV
e
u
+5.1 eV
-14.9 eV
-21.7 eV
1
g
2
u
1
u
H
6
cyclic
linear
+2.8 eV
3
g
+4.6 eV
e
2g
-8.8 eV
2
g
b
2u
6.5 eV
+5.9 eV
3
g

So there we have the cylic and linear polyhydrogens. These AM1 results differ from simplistic one-electron LCAO theory
the main difference is that in one-electron theory, electrons are added and removed with no change in orbital energy,
which is overly simplistic. The basic topologies are important ones that we will see repeatedly in this course.

Note also that the symmetry labels of the orbitals change from one point group to another, but the relationship between
related orbitals is easily recognized from the topologies. We will use these topological patterns at several times during this
course, and they form the basis of the s-type symmetry-adapted orbitals developed in Appendix 4.
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2. a) Use HyperChem to build a model of H
2
S, and minimize it in the AM1 semi-empirical model. What are the bond
lengths and angle? Sketch the atomic energy levels and all the valence molecular orbitals in H
2
S using HyperChem as
a tool. Your final picture should include the energy levels of all the AO and MOs, and topological sketches of the
MOs. What is the bond-order expected to be in your molecule (overall bond order, and bond order per bond)?

We start with a full diagram for the AM1 minimized H
2
S geometry, which has quite a small bond angle. We put the
AOs in reasonable position based on relative electronegativity:
We need to contrast the bonding in
H
2
S with that in water (in your notes). The
primary difference is that the S atomic
orbitals are closer in energy to that of H
than the O atomic orbitals in water. First,
we expect the overlap to be better (more
covalence). This is actually countermanded
somewhat by the greater disparity in orbital
size, so that in fact the overall strength of
the bonds is weaker in H
2
S, although they
are definitely less polar.
The lower polarity reduces the charge
disparity; sulfur is less negative than
oxygen is in water, so hydrogen sulfide is a
weaker Brnsted base than water.
What is not so easy to explain is the
greater bond angle in H
2
S it is in fact due
to greater mixing between 3a
1
and 2a
1
.
Evidence for this is that the gap between b
1

and 2a
1
is larger in H
2
S than in H
2
O (both
in AM1 and in the PES). Since lowering 2a
1
only occurs by bending the molecule, the driving force for greater
bonding is the stabilization of 2a
1
.

b) Now force H
2
S to be linear (Select the bond angle; then use Build Constrain to Linear, and Model Build). Do a
single point AM1 calculation of the linear version of the molecule. Now construct a graph linking the MOs of linear
and angular H
2
S (this kind of graph is known as a Walsh diagram). Use your diagram to explain why hydrogen
sulfide adopts the geometry it does.
Walsh diagram for H
2
S at the AM1 level of theory
1a
1
b
1
1b
2
2b
2
Bond length = 1.34 ;
bond order = 2; 1 per S-H bond
-19.7 eV
-15.4 eV
-12.2 eV
-9.5 eV
+0.9 eV
1.7 eV
2a
1
3a
1
bent
linear
-18.6 eV
-17.6 eV
-1.69 eV
3.3 eV
1
g
2
g
1
u
2
u

u
-9.7 eV

We see that in the bent form, the orbital 2a
1
is stabilized from a completely n.b. orbital of -symmetry, lowering the
total energy of the molecule. Now the bonds are distributed between the 2a
1
and 1b
2
orbitals, which have partial bond
character. The PES bears this out with (A) a sharp peak at 10.6 for the completely orthogonal b
1
orbital, ionization
from which does not change the bond length or angle. And (B) peaks at 13.5 and 15.5 eV for the 2a
1
and 1b
2

orbitals, which have vibrational fine structure, and therefore result in changes in either bond length or angle. Again, as
in H
2
O, ionization of a primarily non-bonding orbital such as 2a
1
will still change the bond angle significantly (imagine
removing one electron from an approximately sp
2
hybridized orbital containing a lone pair.
3. a) Use HyperChem to build a model of BH
3
, and minimize it in the AM1 semi-empirical model. What are the bond
lengths and angle? Sketch the atomic energy levels and all the valence molecular orbitals in BH
3
using HyperChem as
H
2
S at the AM1 level of theory
1a
1
b
1
1b
2
2b
2
Bond length = 1.32 ; bond order = 2.5; 1.25 per S-H bond
-19.7 eV
-15.4 eV
-12.2 eV
-9.5 eV
+0.9 eV
1.7 eV
H SAO's
S
-9.5 eV
-15 eV
2a
1
3a
1
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a tool. Your final picture should include the energy levels of all the AO and MOs, and topological sketches of the
MOs. What is the bond-order expected to be in your molecule (overall bond order, and bond order per bond)?

My calculations for neutral BH
3
give the following energies (AM1 method): 1a
1
21.8; 1e 11.9; 1a
2
+1.6; 2 a
1

+2.7; 2e +5.8 eV. The orbitals are all double occupied up to 1e (6 electrons in total). The bond order is [6 0] =3
or a BO of 1 per BH bond. Note that the LUMO is the unhybridized p
z
orbital on the Boron atom. This is the
acceptor orbital when BH
3
acts as a Lewis Acid. This is the most common reaction that BX
3
compounds undergo. The
bond length is 1.19 , and the bond angles are all 120.

b) Now force BH
3
to be pyramidal (Select all three bond angles; then use Build Constrain to tetrahedral, and Model
Build). Do a single point AM1 calculation of the pyramidal version of the molecule. Now construct a graph linking
the MOs of planar and pyramidal BH
3
(this kind of graph is known as a Walsh diagram). Use your diagram to
explain why boron hydride adopts the geometry it does.

In the Walsh diagram, the planar BH
3
is shown at the right-hand side, and the pyramidal form is at the left. Compare
the schematic orbitals for pyramidal BH
3
with your HyperChem calculations (with ideal tetrahedral angles HBH.)
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The orbitals change their label on traversing the change in bond angle, so it is important to look at the shapes to make
sure that you track the same species. The planar orbitals shown are 1a
1
, degenerate 1e (HOMO) and empty 1a
2

(LUMO). These correspond to the following C
3v
orbitals: 1a
1
, degenerate 1e and 2a
1
. In the pyramidal form, the
energies are 1a
1
22.38; 1e 11.62; 2a
1
+0.2 eV. This corresponds quite clearly to a spot along the Walsh diagram
shown above where the grey vertical line is drawn.

We can now say quite definitively: an AH
3
molecule will be most stable in the planar form if it has six electrons,
because that will fill the 1a
1
and 1e orbitals and leaves the high-energy 1a
2
orbital empty. However, filling this latter
orbital with either one or two electrons is expected to drive the shape towards pyramidal because of the great
stabilization that occurs for the 2a
1
orbital on bending.

4. Use HyperChem to build a model of CH
4
, and minimize it in the AM1 semi-empirical model. What are the bond
lengths and angle? Sketch the atomic energy levels and all the valence molecular orbitals in CH
4
using HyperChem as
a tool. Your final picture should include the energy levels of all the AO and MOs, and topological sketches of the
MOs. What is the bond-order expected to be in your molecule (overall bond order, and bond order per bond)?
Correlate your results to the PES provided (next page).

The geometry has CH of 1.11 and ideal tetrahedral angles. The calculated energies (AM1 level) are: 1a
1
28.9; 1t
2

13.3; 2t
2
+4.7; 2a
1
5.18 eV (note that AM1 places the 2a
1
above 2t
2
; since the energies of empty orbitals are extremely
susceptible to calculational method, this discrepancy is immaterial.) The orbitals are double occupied to the 1t
2
level (8
electrons in total). Note the t type symmetry label, indicating triply degenerate sets of wavefunctions. Such symmetry is
only seen for cubic and higher point groups. The bond order is
[8 0] =4 or BO=1 per CH bond. However, contrary to simple
VB theory, the four CH bonds in methane are not identical. 6
electrons are in the HOMO, and two in the much-lower lying 1a
1

orbital. For verification of this surprising result, we turn to the
UV-PES spectrum shown at right. Indeed, there is a large peak
(indicating lots of emitted electrons) corresponding to ionization
from a level at about 13 eV, and a small peak (fewer electrons)
corresponding to a 23 eV level. This is an amazing fit to the
AM1 calculational result, and clearly shows the correctness of the
delocalized MO description of the bonding in methane. In fact,
the VB orbitals we commonly use are non-orthogonal, and thus
not strictly valid solutions to the Schrdinger equation. They can
be obtained by taking linear combinations of the four orbitals
shown in the diagram above.
5. Use HyperChem to build a model of PH
3
, and minimize it in the AM1 semi-empirical model. What are the bond
lengths and angles? Sketch the atomic energy levels and all the valence molecular orbitals in PH
3
using HyperChem
6-10
as a tool. Your final picture should include the energy levels of all the AO and MOs, and topological sketches of the
MOs. What is the bond-order expected to be in your molecule (overall bond order, and bond order per bond)?

PH
3
at the AM1 level of theory
1a
1
1e
2e
Bond length = 1.36 ; bond angle 96.4 deg; bond order = 3; 1 per P-H bond
-21.3 eV
-13.0 eV
-10.4 eV
H SAO's
N
-10 eV
-18 eV
2a
1
3a
1
a
1
e
2a
1
1a
1
3a
1
1e
2e


In PH
3
, the bond angles are much sharper than they are in NH
3
. In this way, it closely resembles H
2
S compared to
H
2
O. This results in the 2a
1
orbital becoming a very clearly non-bonding orbital with a high degree of phosphorus s
character.

Again, just as in the H
2
S case, this pyramidalization in which the 2a
1
orbital becomes stabilized (see the Walsh diagram
for question 3) is actually driven by mixing with the 3a
1
level. As the 3a
1
becomes more strongly antibonding (it is
indeed extremely antibonding in PH
3
, 2a
1
becomes more an more a lone-pair, non-bonding type of orbital, despite the
fact that it is becoming stabilized. The strongly localized lone-pair character of the LUMO accounts for the excellent
Lewis basicity of phosphine. Its unusually low Brnsted basicity is easily explained by considering the
electronegativity of P and H, which are almost identical. Thus the charge calculated on P is only 0.04 by AM1, versus
0.4 units on the nitrogen atom of ammonia.
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6. Multiple bonds. Use HyperChem to build a model of CO
2
, and minimize it in the AM1 semi-empirical model. What
are the bond lengths and angle? Sketch the atomic energy levels and all the valence molecular orbitals in CO
2
using
HyperChem as a tool. Your final picture should include the energy levels of all the AO and MOs, and topological
sketches of the MOs. What is the bond-order expected to be in your molecule (overall bond order, and bond order per
bond)? Correlate your results to the PES provided (next page).

A schematic orbital
energy level diagram
is provided on this
page, along with the
PES for reference.
The shapes of the
orbitals are given on
the diagram on the
next page.

Both AM1 and the
PES tell us that the
first order interaction
diagram shown here
must be modified.
Thus 1
g
and 1
u
both
gain bond character
and hence 2
g
and 2
u

lose bond character to
become primarily non-
bonding (lone pair)
orbitals.

In this linear
molecule, sharp PES
bands mean non-
bonding MOs, and
broad or split bands
mean bonding or anti-
bonding orbitals.
There is excellent
agreement between
the AM1 orbital
energies and the PES
data. Thus the 1
g

orbitals are completely
non-bonding, and
correspond to p-type lone pair orbitals
localized on oxygen. 1
u
is a doubly
degenerate set of orbitals spreading over the
whole OCO linkage.

The bond order is [8 0] =4, or two per
C=O bond. However, unlike the VB
treatment, there are two bonds extending
over the whole length of the molecule!

8-10

9-10

7. More multiple bonds. Use HyperChem to build a model of ethene, and minimize it in the AM1 semi-empirical model.
What are the bond lengths and angle? Now construct an energy level diagram for ethene in the following manner: (1)
use AM1 to model a carbene fragment, i.e. CH
2
. Specify a triplet ground state. Answer ignore to the warning
about minimizing a triplet it works well enough in this case. Then construct a diagram that correlates the orbitals in
two carbene fragments with the orbitals in ethene. Note that the symmetry labels will not be the same, since the point
groups of carbene and ethene are different. Therefore use your own judgment to decide which orbitals are symmetry
related to one another. In this way, sketch the atomic energy levels and all the valence molecular orbitals in ethene
using HyperChem as a tool. Your final picture should include the energy levels of all the AO and MOs, and
topological sketches of the MOs. What is the bond-order expected to be in your molecule (overall bond order, and
bond order per bond)? Correlate your results to the PES provided (next page).

The two CH
2
fragments. In the correct triplet ground state, each has doubly-filled 1a
1
and 1b
2
orbitals, and singly filled 2a
1
and
1b
1
orbitals. Now arrange these on either side of an interaction diagram, and combine them based on the shape of the fragment
orbitals. The labels will change because we are going to move from C
2v
to D
2h
point groups!



10-10


Ethene has 12 electrons in 6 doubly-filled orbitals. The bonding between CH and C-C is mixed together in the
delocalized MO approach. The bond order is [12 0] =6, which correspond to the five and one of the VB
description of ethene.

There is remarkable agreement between AM1 and the PES spectrum. All bands are broad due to bonding character,
but the first band which is ionization from the -HOMO is sharper than the others, in accordance with the idea that the
-bond is less-strongly bonding than the -bonds.