5.

111 Lecture Summary #13 Monday, October 6, 2014

Readings for today: Section 3.8 – 3.11 Molecular Orbital Theory (Same in 5th and 4th ed.)
Read for Lecture #14: Sections 3.4, 3.5, 3.6 and 3.7 – Valence Bond Theory (Same in 5th
and 4th ed).

Topics: I. Molecular orbital theory

A. Homonuclear molecules with MOs originating from s orbitals
B. Homonuclear molecules with MOs originating from s and p orbitals
C. Heteronuclear diatomic molecules
________________________________________________________________________________
I. MOLECULAR ORBITAL (MO) THEORY

In MO theory, valence electrons are over the entire molecule, not

confined to individual atoms or bonds, as in Lewis and valence-bond models.

Molecular orbitals ( ) of diatomic molecules arise from adding

together (superimposing) atomic orbitals.

A Linear Combination of Atomic Orbitals (LCAO) creates molecular orbitals (bonding

orbitals and antibonding orbitals)

N molecular orbitals can be constructed by N atomic orbitals.

A. Homonuclear molecules with MOs originating from s orbitals

Bonding orbitals arise from LCAO under conditions of constructive interference

σ: designates a molecular orbital that

is cylindrically symmetric about the
bond axis (with no nodal plane along
the bond axis).

+ = σ1s ≡ bonding molecular orbital (MO) and also a wavefunction.

When waves interfere constructively, the amplitude increases

where they overlap.

Increased amplitude in the internuclear region translates to an

enhanced probability density (ψ2) between the nuclei.
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Any electron that occupies a bonding MO will be attracted to BOTH nuclei, and therefore
will be compared to an atomic orbital associated with a
single nucleus.
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Energy of interaction. The energy of a bonding orbital is compared to
the atomic orbitals!

For H2, when its two electrons both occupy the bonding orbital, the molecule is
stable.

Antibonding orbitals (result of destructive interference of two atomic orbitals)

- = σ1s* ≡ antibonding molecular orbital.

When wavefunctions interfere destructively, the amplitude

decreases where they overlap.

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Decreased amplitude in the internuclear region translates to a diminished probability

density (ψ2) between the nuclei and a node between the two nuclei.

An electron in this antibonding orbital would be essentially excluded from

the internuclear region, and thus have a energy than if in an atomic
orbital.

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Energy of interaction. The energy of an antibonding orbital is
compared to the atomic orbitals!

An antibonding orbital is raised in energy by approximately the same amount that the
bonding orbital is lowered in energy.

N molecular orbitals can be constructed by N atomic orbitals. Thus, 2 atomic orbitals

generate 2 molecular orbitals (one bonding and one antibonding, one lower in energy
and one higher in energy).

MO diagram of H2: In the case of H2, both electrons are in the σ1s orbital.

Electron configuration of H2:

MO diagram of He2:

Electron configuration of He2:

There is in
energy for He2 compared to 2 He.

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MO theory predicts He2 does not exist because no net gain in E.

BOND ORDER = ½ (# of bonding electrons - # of antibonding electrons)

He2: (σ1s)2(σ1s*)2

bond order = bond

H2: (σ1s)2

bond order = bond

Reality: He2 does exist. ‘Discovered’ in 1993. Weakest chemical bond known.
∆Ed = 0.01 kJ/mol for He2
∆Ed = 432 kJ/mol for H2

The MOs formed by LCAO for 2s orbitals are analogous to those formed by 1s.

Li2

Electron configuration: (σ1s)2(σ1s*)2(σ2s)2

Bond order: ½ ( )=

∆Ed = kJ/mol

Note: Bond order can be calculated by considering all electrons or only valence electrons.

Be2

e- configuration: (σ1s)2(σ1s*)2(σ2s)2(σ2s*)2

Bond order (counting all electrons):

½( )=

Bond order (counting only valence e-s):

½( )=

∆Ed = kJ/mol - very weak

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B. Homonuclear molecules with MOs originating from s and p orbitals

Bonding MOs formed by LCAO of 2px and 2py as a result of constructive interference

Bond axis and nodal plane

2pxa + 2pxb = π2px

or or
2pya + 2pyb =

π-orbital: Molecular wavefunction (molecular orbital) with a nodal plane through the
axis.

Antibonding MOs formed by LCAO of 2px and 2py as a result of destructive interference

2pxa - 2pxb =
or or
2pya - 2pyb =

π*-orbitals: Molecular wavefunction (molecular orbital) with TWO nodal planes. One
nodal plane is through the bonding axis and the other is between nuclei.

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Please note that MO diagrams for B2 and C2 below are incomplete since they do not
include the 2pZ molecular orbitals!

Valence electron configuration: Valence electron configuration:

Bond order = ½ ( 4 - 2 ) = Bond order = =

Just considering 2s, 2px, and 2py for the moment, let’s sum it up:
Two 2s AOs generate two σ2s MOs (lower energy σ2s & higher energy σ2s*).
Two 2px AOs generate two 72px MOs (lower energy 72px & higher energy 72px*).
Two 2py AOs generate two 72py MOs (lower energy 72py & higher energy 72py*)

The stability of the resulting molecule depends on the # electrons that occupy lower
energy orbitals compared to the # that occupy higher energy orbitals.

If the net result of molecule formation is that more electrons have a lower energy, then
the molecule is .

If the energy differential is small, then the molecule is not as stable.

For B2: (σ2s)2(σ2s*)2 π2px π2py * For C2: (σ2s)2(σ2s*)2 (π2px)2 (π2py*)2
e- in lower energy (bonding orbital) e- in lower energy (bonding orbital)
e- in higher E (antibonding orbital) e- in higher E (antibonding orbital)

Bond order = ½(4-2) = 1 Bond order = ½(6-2) = 2

∆Ed = ∆Ed =

Please note that complete MO diagrams for B2 and C2 must include the 2pZ molecular orbitals
even if no electrons are in those orbitals.

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Bonding MOs formed by LCAO of 2pz

σ: cylindrically symmetric with

no nodal plane about the bond
axis
2pza + 2pzb =

Nodes pass through nuclei, but no nodes along the bond axis.

Constructive interference results in a region of increased amplitude between nuclei, and

thus an increased probability density between nuclei (therefore lower energy MO)

Antibonding MOs formed by LCAO of 2pz

σ: cylindrically symmetric with no

nodal plane about the bond axis

2pza - 2pzb = σ2pz*

Nodes pass through and between the nuclei, but no nodes along the bond axis.

Destructive interference results in a nodal plane between the nuclei, and decreased
probability density between nuclei (therefore higher energy MO)

The relative energies of the σ2pz orbital compared to the π2px and π2py orbitals depend
on the value of the atoms.

For simple homonuclear diatomic molecules:

• The relative E ordering is (π2px) and (π2py) < (σ2pz) if Z < .

• The relative E ordering is (σ2pz) < (π2px) and (π2py) if Z = or > .
• The relative E ordering of antibonding orbitals doesn’t change with Z.

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(σ1s)2(σ1s*)2(σ2s)2(σ2s*)2(σ2pz)2(π2px)2(π2py)2 (σ1s)2(σ1s*)2(σ2s)2(σ2s*)2(π2px)2(π2py)2(σ2pz)2
(π2px*)1(π2py*)1

B.O. = ∆Ed = 494 kJ/mol B.O. = ∆Ed = 941 kJ/mol

O2 is a ! Two unpaired No unpaired electrons (diamagnetic)
electrons (paramagnetic)

MO theory does a better job describing the properties of O2 than Lewis Structures do.
Both MO theory and Lewis Structures do a good job with N2.

Note: Molecules possessing unpaired electrons are paramagnetic (attracted by magnetic

field); those in which the electrons are paired are diamagnetic (repelled by magnetic
field).

C. For HETERONUCLEAR diatomic molecules:

• The relative E ordering is (π2px) and (π2py) < (σ 2pz) if Z < 8 for both atoms.
• You are NOT responsible for predicting the energy level ordering if either one of
the atoms has Z = or > 8.

For full credit on MO diagrams,

 label increasing energy with an arrow next to the diagram.
 pay attention to whether the question asks for valence electrons or all electrons.
 for any bonding orbital drawn, include the corresponding anti-bonding orbital,
even if it is not filled with any electrons.
 label each atomic orbital (1s, 2s, 2px, 2py, etc.) and each molecular orbital (⌠2s, 72px,
72py, etc.) that you draw.
 fill in the electrons for both the atomic and molecular orbitals.

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5.111 Principles of Chemical Science

Fall 2014

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