Assignment CM1101

5% CA.

Select one of the molecules from (i) to (iii) below and use either (a) Lewis and VSEPR to

determine the structure (estimating all angles and providing the structure) then apply

either VB theory, (b) combined VB-MO theory (covered in Lecture XVI), or (c) MO

theory to determine the MOs for any of the molecules (i) to (iv). If you choose VB-MO

theory (covered in Lecture XVI), or MO theory then you must construct an MO energy

level diagram and provide the electronic configuration. If you choose MO theory you

must provide the point group and the symmetry of all the orbitals. You will need to show

how you determined the symmetry of the orbitals.

(i) F2O, (ii) BeF2, (iii) AlCl3, or (iv) I3- (NB: Only MO theory can be applied to I3-

molecule)

 Students who choose VB theory will receive a maximum of 3% toward their CA

for the assignment.

 Students who choose combined VB-MO theory will receive a maximum of 4%

toward their CA for the assignment.

 Students who choose MO theory can receive a maximum of 5% toward their CA

for the assignment.

There is no page limit.

Your assignment is due on Monday the 12th of November, before midnight and is to

be submitted via soft-copy to the IVLE.

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TIP for those who choose MO theory for AlCl3. When you decide on the point group,

you will need to classify the symmetry of the valance AOs of the Al and Cl atoms. There

is no need to consider what the S3 operation does (not considered in this module) as you

can classify the symmetry of the AOs without using it. We also have not learnt how to

classify the symmetry for groups of orbitals when we need to group more than two

orbitals together. For AlCl3, we need to group together sets of AOs for the Cl atoms, so I

will provide you with the symmetries of these group orbitals:

• The 3 Cl 3s AOs are combined into group orbitals with the symmetries:

a1’ ⊕ e’

• The 3 Cl 2pz AOs are combined into group orbitals with the symmetries:

a2” ⊕ e”

• The 3 Cl 2px and 2py AOs are combined into group orbitals with the symmetries:

a1’ ⊕ a2’ ⊕ e’ ⊕ e’

Note that e symmetry orbitals are doubly degenerate (just like π symmetry orbitals in

linear molecules), i.e., e’ and e” orbitals. However, just because they are doubly

degenerate does not at all imply that they are π -bonds, only that they are two equivalent

orbitals like px and py in linear molecules or px, py and pz in atoms etc.

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F2O

According to Lewis and VSEPR, the structure of F2O is bent, and its point group is C2v.

The axes are defined as follows:

The character table for C2v is as follows:

Symmetry E C2 σ (xz) σ (yz)

A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1

The classification of the symmetry of the orbitals is as follows:

Orbital E C2 σ (xz) σ (yz) Symmetr

y
O 2s 1 1 1 1 a1
O 2pz 1 1 1 1 a1
O 2py 1 -1 -1 1 b2
O 2px 1 -1 1 -1 b1
Fa 2s + Fb 2s 1 1 1 1 a1
Fa 2s - Fb 2s 1 -1 -1 1 b2
Fa 2pz + Fb 2pz 1 1 1 1 a1
Fa 2pz - Fb 2pz 1 -1 -1 1 b2
Fa 2py + Fb 2py 1 -1 -1 1 b2
Fa 2py - Fb 2py 1 1 1 1 a1
Fa 2px + Fb 2px 1 -1 1 -1 b1
Fa 2px - Fb 2px 1 1 -1 -1 a2

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The ionization energy of F is 17.41 eV, and O is 13.58 eV. According to the document

“AO Energies Period 1-2.doc” in the Extra workbin the energy of the 2s of F and O

respectively are 40 and 33 eV.

The MO diagram is thus:

5a1
2b1
4b2

a1, b1, b2
2p
4a1, 3b2, 1a2 a1, a1, b2, b2, b1, a2
O 2p

2b2 2F
1b1
3a1

2a1

a1
2s
O 1b2 a1, b2
2s
2F

1a1

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1) The order of the MOs from the p AOs is uncertain, thus the symmetry of the

HOMO is uncertain, but is one of a1, b1 or b2 symmetries.

2) The sp energy gap of F and O is too large for there to be significant sp mixing.

3) When we interact 3 orbitals of the same symmetry, 1 will be bonding, 1 will be

nonbonding and the remaining is anti-bonding.

4) F2O possess 20 valence electrons and has the electronic configuration:

a. KKK(1a1)2(1b2)2(2a1)2(3a1)2(1b1)2(2b2)2(4a1)2(3b2)2(1a2)2(4b2)2

b. Filled bonding MOs are: 1a1, 3a1, 1b1, 2b2.

c. Filled nonbonding MOs are: 1b2, 4a1, 3b2, 1a2.

d. Filled antibonding MOs are 2a2, 4b2.

5) BO is ½ (8 – 4) = 2.

6) Note: Sketches should be provided of the MOs in order to clearly demonstrate the

character under the various symmetry operations given in the second Table.

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BeF2

According to Lewis and VSEPR, the structure of BeF2 is linear, and its point group is

D∞h.

The classification of the symmetry of the orbitals is as follows:

Orbital E i Symmetr
y
Be 2s 1 1 σg
Be 2pz 1 -1 σu
Be 2py,x 2 -1 π u
Fa 2s + Fb 2s 1 1 σg
Fa 2s - Fb 2s 1 -1 σu
Fa 2pz + Fb 2pz 1 -1 σu
Fa 2pz - Fb 2pz 1 1 σg
Fa 2py,x + Fb 2py,x 2 -1 π u
Fa 2py,x - Fb 2py,x 2 1 π g

The ionization energy of F is 17.41 eV, and Be is 9.33 eV. According to the document

“AO Energies Period 1-2.doc” in the Extra workbin the energy of the 2s of F is at 40 eV.

The energy of the p AOs in Be can not be too much larger than the energy of the 2s AO,

since the sp energy gap for group IIIA is not large.

Note: Sketches should be provided of the MOs in order to clearly demonstrate the

character under the various symmetry operations given in the Table.

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The MO diagram is thus:

σ u, 3σ u
2π u
2p 4σ g
π u

σ 3σ g

2s g
Be

σ g, σ u, π g,
1π g
1π u
π u 2p
2σ u
2σ g

σ g, σ u

1σ g, 2s
2F
Way down in energy
1σ u

1) The 2s AO of the Fs are too low in energy to interact with Be AOs.

2) The 2s AO of Be interacts marginally with the 2pz AOs σ g group orbital on the

Fs.

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3) The 2p AO of Be interacts even less than in (2) so that the 1π u and 2σ u formally

“bonding” MOs are for all practical purposes a nonbonding MO localized on both

F’s.

4) The π g group MOs derived from F’s p AOs are strictly nonbonding.

5) BeF2 possess 16 valence electrons and has the electronic configuration:

a. KKK(1σ g)2(1σ u)2(2σ g)2(2σ u)2(1π u)4 (1π g)4

b. Filled bonding MOs: 2σ g (and formally) 1π u and 2σ u

c. Filled nonbonding MOs: 1σ g, 1σ u,1π g

d. No filled antibonding MOs.

e. BO (formally) ½ (8 – 0)/2 = 4, but for all practical purposes, the 1π u and

2σ u MOs are essentially nonbonding, so that the BO is only 1. Worse,

the 2σ g MO is also not particularly strongly covalent, with most of the

electron density localized on the F’s. The BeF2 is fairly weakly covalently

bonded. This is to be expected when a metal bonds with a nonmetal.

f. Note that while BeF2 is not strongly covalently bonded we predict it to be

very strongly ionically bonded since all of the valence electrons are

essentially localized on both F’s, with little significant electron density on

Be. Thus BeF2 is basically, F-(Be2+)F-.

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AlCl3

According to Lewis and VSEPR, the structure of AlCl3 is trigonal planar, and its point

group is D3h.

The axes are defined as follows:

The character table for D3h is as follows:

Symmetry E 2C3 3C’2 σh 2S3 3σ v

A’1 1 1 1 1 1 1
A’2 1 1 -1 1 1 -1
E’ 2 -1 0 2 -1 0
A”1 1 1 1 -1 -1 -1
A”2 1 1 -1 -1 -1 1
E” 2 -1 0 -2 1 0
The classification of the symmetry of the orbitals is as follows. Note that the symmetry

classifications for Cls group orbitals have already been provided to you in the

assignment. Note also that we ignore the S3 operation as we have not learnt (nor do we

need it here) about this yet.

Orbital E 2C3 3C’2 σ h 3σ v Symmetr

y
Al 2s 1 1 1 1 1 a'1
Al 2pz 1 1 -1 -1 1 a''2
Al 2py,x 2 a 0 2 0 e'

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a
We also haven’t learnt how to deal with this situation either, but as it turns out we don’t

need to know the character under this operation. We can classify these orbitals without

it. The px and py orbitals must have e' symmetry.

The ionization energy of Al and Cl are 5.99 eV and 12.97 eV respectively. The sp gap

for Cl is very large compared to Al, so the 3s AO of Cl will not partake in chemical

bonding.

The MO diagram is thus:

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 2a''2
4e'
a''2 ⊕ e'
3p

3a'1
a'1
3s
Al
2σ u,

1π g
3e'
a''2 ⊕ e'' (pz)
1e''⊕1a'2⊕3e' a'1 ⊕ a'2 ⊕ e' ⊕ e' (px,y )
3p
2e'
1a''2
2e' 2a'1

a'1 ⊕ e'

3Cl 3s
1a'1⊕1e' Way down in energy

1) The 3s AO of the Cls are too low in energy to interact with Al AOs.

2) 2e' and 3e' interact and form bonding and non-bonding MOs

3) AlCl3 possess 24 valence electrons and has the electronic configuration:

a. KKKKLLLL(1a'1)2(2e')4(2e')4(2a'1)2(1a''2)2(1e'')4(1a'2)2(3e')4

b. Filled bonding MOs: 2e', 2a'1, 1a''2

c. Filled nonbonding MOs: 1a'1, 1e', 1e'', 1a'2, 3e'

d. There are no filled antibonding MOs.

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e. Bond order: ½ (8 – 0) = 4. However, electron density is largely, but not

completely localized on the Cl atoms. So while there is significant

covalency in AlCl3 the molecule will largely be held together by ionic

bonding.

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I3-

According to Lewis and VSEPR, the structure of I3- is linear, and its point group is D∞h.

The classification of the symmetry of the orbitals is as follows:

Orbital E i Symmetr
y
I (central) 5s 1 1 σg
I (central) 5pz 1 -1 σu
I (central) 5py,x 2 -1 π u
Ia 2s + Ib 2s 1 1 σg
Ia 2s - Ib 2s 1 -1 σu
Ia 2pz + Ib 2pz 1 -1 σu
Ia 2pz - Ib 2pz 1 1 σg
Ia 2py,x + Ib 2py,x 2 -1 π u
Ia 2py,x - Ib 2py,x 2 1 π g

Note: Sketches should be provided of the MOs in order to clearly demonstrate the

character under the various symmetry operations given in the Table.

The MO diagram is thus:

3σ u

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 2π u σ g, σ u, π g,
σ u,
3σ g,
π u
5p π 5p
u
1π
1π g
u

2σ u
Group VIIA - large
sp gap.
2σ g

σ
σ g, σ
5s 1σ u
u
5s
g

I (central) 1σ g
2I (outter)

1) I3- possess 22 valence electrons and has the electronic configuration:

a. KKKLLLMMMNNN(1σ g)2(1σ u)2(2σ g)2(2σ u)2(1π u)4(3σ g)2(1π g)4(2π

u)4

b. Bonding MOs filled: 1σ g, 2σ u, 1π u.

c. Nonbonding MOs filled: 1σ u, 3σ g, 1π g.

d. Antibonding MOs filled: 2σ g, 2π u.

e. Bond order: ½ (8 – 6) = 1. A weakly bound 100% covalently bonded

system.

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