CHEMISTRY 2000

Topic #1: Bonding – What Holds Atoms Together?

Fall 2020
Dr. Susan Findlay
See Exercises 4.1 to 4.6
Taking MO Theory Past the Diatomics

 Molecular orbital theory is valid for all molecules. Thus far, we’ve
focused on the diatomics because it’s only convenient to manually
derive complete MO diagrams for molecules that are either very
small or highly symmetric.
 It was easier for us to predict MOs for symmetric molecules (like
O2) than asymmetric molecules (like CO). For this reason, our
studies of larger molecules will be confined to highly symmetric
ones – like BeH2, CO2 and C6H6. Computers are used to predict
MOs for less symmetric molecules (“computational chemistry”).
 The principles used to predict MOs and MO diagrams for the
diatomics are the same as those used for larger molecules.
 Continue to look for valence atomic orbitals with:
 COMPATIBLE SYMMETRY (σ vs. π)

 COMPATIBLE ENERGY (as close as possible; no farther apart

than ~ 1 Ry)
 Make sure you make the same number of MOs as you had AOs!
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 Keep electron distribution in MOs symmetric if molecule is symmetric.
Molecular Orbitals for BeH2

 BeH2 is the simplest triatomic molecule. In the gas phase, it is

linear (as we’d expect from the Lewis structure):

 The relative energies for the atomic orbitals of Be and H are:

 1s (Be) = -9.38 Ry ▪ 1s (H) = -0.99 Ry
 2s (Be) = -0.61 Ry
 2p (Be) = +0.14 Ry

 Which valence atomic orbitals can combine to make σ MOs?

 Which valence atomic orbitals can combine to make π MOs?

 Which valence atomic orbitals will not combine at all (leaving

them as either σ or π nonbonding MOs)?
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Molecular Orbitals for BeH2

 We are combining four σ-symmetric AOs to make four σ-MOs.

To predict what these four MOs will look like, we use symmetry
and an increasing number of nodes:

 The overall shape (i.e. shape of the lobes) for every MO in the
set must share the symmetry of the overall molecule. If the
molecule is nonpolar, none of the MOs should be “lopsided”! 4
Molecular Orbitals for BeH2

 To predict the energies of a set of MOs:

 The lowest energy σ-MO is lower in energy than all AOs from which
it’s made.
 The highest energy σ-MO to be higher in energy than all the AOs
from which it’s made.
 Use these two MOs and the energies of the AOs that were used to
build the set of MOs to estimate the energies of the middle MOs.

 As in the MO diagrams for diatomics, the MOs are tracked in the

middle of the diagram with the AOs at the sides. Equivalent
atoms (such as the Hs in BeH2) are grouped at one side, making
sure to include all their valence AOs (one 1s AO for each H).

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 Molecular Orbitals for BeH2

2p

2s

1s
Energy

Be H (x2)
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 Molecular Orbitals for BeH2

4σ

3σ
2p 1π

Energy 2s

2σ 1s

1σ

Be BeH2 H (x2)
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Molecular Orbitals for BeH2

 When you calculate bond order for bonds in polyatomic

molecules, it’s essential to account for the number of “bonds”
(atom-to-atom connections) over which the electrons are
distributed.

 How many Be-H bonds share the bonding electrons in BeH2?

 Compare the bond order predicted by the Lewis diagram for BeH2
to the bond order calculated from the MO diagram.

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Molecular Orbitals for BeH2

 What is the Highest Occupied Molecular Orbital for BeH2?

 What is the Lowest Unoccupied Molecular Orbital for BeH2?

 Is BeH2 more likely to react as a Lewis acid or a Lewis base?

Use the energies of the HOMO and LUMO to justify your choice.
Use the shape of the relevant MO to show the most likely
reactive site in BeH2.

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Molecular Orbitals for CO2

 CO2 may not appear much more complicated than BeH2 – both
of them being linear triatomic molecules – but it has rather
more valence orbitals to consider. As usual, we will divide the
atomic orbitals by symmetry:

σ-symmetric π-symmetric

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Valence Molecular Orbitals for CO2

 The six π-symmetric AOs can be subdivided into two sets:

the 2px AOs and the 2py AOs. Each of those sets can be
combined to make three MOs.

 Use symmetry and nodes to predict the shapes of these MOs

and their relative energies:

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Valence Molecular Orbitals for CO2

 The six σ-symmetric AOs can be treated as a group and

combined to make six σ-symmetric MOs. Symmetry and nodes
can be used to predict their shapes and relative energies:

 Find the perpendicular nodes in these MOs to convince yourself

that they are in the correct order by energy. Can you work out
which atomic orbitals each might have been made from? 12
Valence Molecular Orbitals for CO2

 A computer shows us the relative energies of all these MOs:

6σ

5σ
3π

2p
2π
Energy 2p
1π
2s 4σ
3σ

2σ 2s
1σ
C CO2 O (x2)
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Valence Molecular Orbitals for CO2

 Complete the MO diagram on the previous page:

 Fill in the electrons.
 To the best of your ability, label each MO as bonding, antibonding
or nonbonding.

 Write the valence orbital occupancy for CO2.

 Use the MO diagram to calculate the average C-O bond order.

Compare it to the bond order predicted by the Lewis diagram.

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Valence Molecular Orbitals for CO2

 Use the frontier molecular orbitals (the HOMO and LUMO) to

predict how CO2 will react.
 Identify the HOMO. When CO2 acts as a Lewis base, which atom(s)
donate the electron pair, and is bond order affected?

 Identify the LUMO. When CO2 acts as a Lewis acid, which atom(s)
accept the electron pair, and is bond order affected?

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Valence Molecular Orbitals for CO2

 What is the main difference between the picture of CO2

provided by MO theory and the picture of CO2 provided by the
Lewis structure?

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MO Theory and Delocalized π Electrons
 Once we move beyond the linear triatomics, the σ-MOs quickly
become relatively complicated and difficult to predict.
e.g. the valence σ-MOs of BH3:

 The π-MOs, on the other hand, are still relatively straightforward

to predict.
e.g. the valence π-MO of BH3:

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MO Theory and Delocalized π Electrons
 Fortunately, the phenomenon of sigma-pi separation means
that we’ve been discussing σ-MOs and π-MOs separately.

 You may have noticed that the HOMO and LUMO in molecules
like CO2 are often both π-MOs. For many molecules (especially
organic ones), it can be quite helpful to focus on the π-MOs
when talking about their properties or reactivity.

 Furthermore, the electrons which appear to “move” between

resonance structures turn out to be electrons in π-MOs. MO
theory demonstrates that those electrons are delocalized.
When you look at the shapes of these π-MOs, you get a better
picture of how those electrons are shared by multiple atoms.

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MO Theory and Delocalized π Electrons
 Removing the σ MOs from our valence MO diagram for CO2 …

6σ

5σ
3π

2p
2π
Energy 2p
1π
2s 4σ
3σ

2σ 2s
1σ
C CO2 O (x2)
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MO Theory and Delocalized π Electrons
 … leaves the valence π MO diagram for CO2:

6σ

5σ
3π

2p
2π
Energy 2p
1π
2s 4σ
3σ

2σ 2s
1σ
C CO2 O (x2)
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MO Theory and Delocalized π Electrons

 Important points to remember:

 We are approximating that, for every bond (single, double or triple),
there are two electrons in σ bonding MOs. This does not mean that
there is a σ-MO focused on the bonding region. It may, for
example, mean that there are three bonding σ-MOs holding
together three different bonds (as shown for BH3 on page 17 – the
three leftmost MOs are all σ-bonding, each containing 2 electrons)
 If an MO spans three or more atoms, the electrons in it are shared
by more than one bond. e.g. a pair of pi bonding electrons in CO2
provides a half bond order to each of the two C-O bonds.
 When discussing bond order, only π bond order can be determined
from a π-MO diagram. The total bond order will therefore be 1
more than the π bond order (since average σ bond order is 1).

Total bond order = π bond order + σ bond order

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MO Theory and Delocalized π Electrons

 Recall that:
 A π MO is bonding if its energy is lower than the average energy of
the p orbitals in the pi system.
 A π MO is nonbonding if its energy is the same as the average
energy of the p orbitals in the pi system.
 A π MO is antibonding if its energy is higher than the average
energy of the p orbitals in the pi system.

 Looking at nodes can also help us categorize MOs. Check if an

MO appears bonding or antibonding in each bonding region.
 If there are more bonding interactions than antibonding
interactions, the MO is net bonding.
 If there are more antibonding interactions than bonding
interactions, the MO is net antibonding.
 If there are the same number of antibonding and bonding
interactions, the MO is nonbonding.
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Resonance and MO Theory: Ozone (O3)

 One of the first molecules for which we drew resonance

structures in CHEM 1000 was ozone:

 The molecular geometry of ozone is _____________________.

ALW AYS check w hether a m olecule is planar or linear.

Linear m olecules have 2 pi system s. P lanar ones have 1!

 Ozone has:
 ____ π-symmetric valence AOs therefore ____ valence π-MOs.
 ____ σ-symmetric valence AOs therefore ____ valence σ-MOs.
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Resonance and MO Theory: Ozone (O3)

 To decide how many electrons go into π-MOs and how many go

into σ-MOs, look at the Lewis diagram.
 Each single bond corresponds to two electrons in σ-MOs
 Each double bond corresponds to two electrons in σ-MOs and two
electrons in π-MOs
 Each triple bond corresponds to two electrons in σ-MOs, two
electrons in one set of π-MOs (one pi system) and two electrons in
another set of π-MOs (another pi system)
 A lone pair on an atom next to a double/triple bond corresponds to
two electrons in π-MOs
 Any other lone pair corresponds to two electrons in σ-MOs

Notice that the lone pairs on atoms next to a double/triple bond

are the ones which move between resonance structures!

 Ozone has:
 ____ electrons in valence π-MOs.
 ____ electrons in valence σ-MOs. 24
Resonance and MO Theory: Ozone (O3)

 Use symmetry and nodes to work out what the π-MOs of ozone
look like, ranking them from lowest to highest energy. Then, fill
in the electrons to give a complete π-MO diagram.

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Resonance and MO Theory: Ozone (O3)

 How does your MO diagram for O3 relate to the Lewis diagrams

you drew for it? Consider both bond order and formal charges.

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Resonance and MO Theory: Benzene (C6H6)

 The classic example of delocalized π electrons and MO theory is

benzene. The Lewis structure of benzene is:
H H

H C H H C H
C C C C

C C C C
H C H H C H

H H

 If we assign molecular geometries to each carbon atom, we see

that benzene is a planar molecule:

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Resonance and MO Theory: Benzene (C6H6)

 Sorting the valence atomic orbitals by symmetry gives

____ σ-AOs and ____ π-AOs.

 Therefore, benzene will have ____ σ-MOs and ____ π-MOs.

 There are ____ electrons in σ-MOs and ____ electrons in π-MOs.

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Resonance and MO Theory: Benzene (C6H6)

 So, we know that benzene has ____ π-MOs containing ____

electrons. We also know that these π-MOs were made by
combining six 2pz orbitals on the six carbon atoms.
 Cyclic molecules tend to have degenerate π energy levels.
 A “quick and dirty” trick to predict the relative energy levels for
cyclic molecules is to draw a circle. Inside the circle, draw a
polygon the same shape as your molecule. Make sure the tip of
the polygon is at the bottom of the circle. The corners of the
polygon are at the same height as the relative energy levels. If
you draw a horizontal line across the middle of the circle
(representing the energy of the p atomic orbitals), all orbitals below
it are bonding and all orbitals below it are antibonding. This
method (a Frost circle) is a huge oversimplification but it works.
H
4π*
H C H
C C 3π*

H
C
C
C
H
E 2π
H 1π
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Resonance and MO Theory: Benzene (C6H6)

 We’ve worked out the energy levels, but what do the MOs look
like? To answer that, we go back to our old standby method –
symmetry and nodes!
 The lowest energy π-MO (1π) has one nodal plane – the one cutting
through the plane of the molecule. It has no nodes perpendicular to
the plane of the molecule.
 Every time you go up to the next energy level, add a node
perpendicular to the plane of the molecule, keeping them as evenly
spaced as possible. If there are two degenerate π-MOs, keep their
nodes as askew as possible (perpendicular if possible, at a 45º angle
as next choice, etc.)
 The highest energy π-MO should be “as antibonding as possible” –
i.e. nodes between every pair of neighbouring atoms

 Once you’ve determined the energy levels and the shapes of the
π-MOs, the last step is to fill in the electrons. Recall that we have
____ π electrons to add to the π-MO diagram. 30
 Resonance and MO Theory: Benzene (C6H6)

H 4π
H
C
C
C
H
E
C C
H C H
3π
H

Energy of
2p AOs

2π

1π

 This MO diagram confirms that benzene can’t be considered to

have “three double bonds and three single bonds”. It really does
have three bonds with bond order _____. This has been proven
experimentally: all six C-C bonds in benzene are 140 pm (whereas
pure C-C bonds are 154 pm and pure C=C bonds are 134 pm). 31