9C.

MO theory: homonuclear diatomic molecules

□ Electron configurations
 In Topic 8C, the hydrogenic atomic orbitals and the building-up
principle are used as a basis for the discussion and prediction
of the ground electronic configurations of many-electron atoms.
 We now do the same for many-electron diatomic molecules by
using the 𝐻 molecular orbitals developed in Topic 9B
as a basis for their discussion.
○ Electron configurations
- The starting point of the building-up principle for diatomic
molecules is the construction of molecular orbitals by combining
the available atomic orbitals.
- Once they are available, we adopt the following procedure,
which is essentially the same as the building-up principle for
atoms (Topic 8B):

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ Electron configurations (cont.)
- Once they are available, we adopt the following procedure.
Building-up principle for molecules
① The electrons supplied by the atoms are accommodated in
the orbitals in order to achieve the lowest overall energy subject to
the constraint of the Pauli exclusion principle, that no more than two
electrons may occupy a single orbital (and then must be paired).
② If several degenerate molecular orbitals are available,
electrons are added singly to each individual orbital before doubly
occupying any one orbital (because that minimizes electron-electron
repulsions).
③ According to Hund‘s maximum multiplicity rule (Topic 8B),
if two electrons do occupy different degenerate orbitals, then
a lower energy is obtained if they do with parallel spins.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals
- Consider H2, the simplest many-electron diatomic molecule.
- Each H atom contributes a 1s orbital (as shown in 𝐻 ), so we can
form bonding 𝜎 and antibonding 𝜎 ∗ orbitals from them, as
explained in Topic 9B.
- At the experimental internuclear separation, these orbitals
will have the energies shown in Fig. 9C.1, which is called
a molecular orbital energy level diagram.
☞ From two atomic orbitals, we can build two molecular orbitals.
※ In general, from 𝑁 atomic orbitals we can build 𝑁 molecular orbitals.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- There are two electrons to accommodate, and both can enter
𝜎 by pairing their spins, as required by the Pauli principle
(as shown in atoms, Topic 8B).
- Therefore, the ground-state configuration is 𝜎 and the atoms
are joined by a bond consisting of an electron pair in a bonding
𝜎 orbital.
- This approach shows that one electron pair, which is the focus
of Lewis’s account of chemical bonding, represents the maximum
number of electrons that can enter one bonding molecular orbital.
 Only one electron pair can enter one bonding molecular orbital
9C. MO theory: homonuclear
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- The same argument explains why Helium does not form molecule.
- Each He atom contributes a 1s orbital, so 𝜎 and 𝜎 ∗ molecular
orbitals can be constructed.
- Although these orbitals differ in detail from those in H2,
their general shapes are the same and we can use the same
qualitative energy level diagram in the discussion.
- There are four electrons to accommodate.
- Two electrons can enter the 𝜎 orbital, but then it is full, and
the next two must enter the 𝜎 ∗ orbital (Fig. 9C.2).
- Therefore, the ground electronic configuration of He2 is 𝜎 𝜎 ∗ .
- We see that there is one bond and one antibond.
- Because 𝜎 ∗ is raised in energy relative to the separate atoms
more than 𝜎 is lowered, an He2 molecule has a higher energy
than the separated atoms, so it is unstable relative to them and
dihelium does not form.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- We will now see how the concepts apply to homonuclear
diatomic molecules in general.
- In basis treatments, only the orbitals of the valence shell are
used to form molecular orbitals, so only the 2s and 2p atomic
orbitals are considered (for molecules formed with atoms from
Period 2 elements).
- A general principle of MO theory is that
All orbitals of the appropriate symmetry contribute to
a molecular orbital.
- Thus, to build 𝜎 orbitals, we form linear combinations of
all atomic orbitals that have cylindrical symmetry about
the internuclear axis.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- These orbitals (which have cylindrical symmetry about
the internuclear axis) are the 2s orbitals on each atom and the
2pz orbitals on each atom (Fig. 9C.3).
- Therefore, the general form of 𝜎 orbitals that may be formed is
𝜓 𝑐 𝜓 𝑐 𝜓 𝑐 𝜓 𝑐 𝜓 (9C.1)
- From these four atomic orbitals, we can form four molecular
orbitals of 𝜎 symmetry by an appropriate choice of
the coefficients 𝑐.
- The procedure for calculating the coefficients is described
in Topic 9D and more fully in Topic 9E.

internuclear axis

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- Here, we adopt a simpler route, and suppose that they may be
treated separately because 2s and 2pz orbitals have distinctly
different energies.
- That is, the four 𝜎 orbitals fall approximately into two sets,
one consisting of two 2s molecular orbitals of eq. 9C.2a form
𝜓 𝑐 𝜓 𝑐 𝜓 (9C.2a)
- and another consisting of two 2pz orbitals of eq. 9C.2b form
𝜓 𝑐 𝜓 𝑐 𝜓 (9C.2b)
- Because atoms 𝐴 and 𝐵 are identical, the energies of
their 2s orbitals are the same, so the coefficients are equal
(apart from a possible difference in sign); the same is true of
the 2pz orbitals.
- Therefore, two sets of orbitals have the form 𝜓 𝜓 and
𝜓 𝜓 , the combination being bonding and
the combination antibonding in each case.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- At this stage it is useful to adopt a more formal system for
denoting molecular orbitals.
- First, the orbitals are labelled with 𝑔 and 𝑢 to indicate their
inversion symmetry, as explained in Topic 9B.
- Then, each set of orbitals of the same inversion symmetry is
numbered separately.
- Therefore, the 𝜎 orbital formed from the 2s orbitals is labelled
1𝜎 and 𝜎 ∗ orbital formed form the same atomic orbitals is
denoted 1𝜎 .

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- Two 2pz orbitals along the internuclear axis overlap strongly.
- They (2pz) may interfere either constructively or destructively, and
give a bonding or antibonding 𝜎 orbitals that lie higher in energy
than the 1𝜎 and the 1𝜎 orbitals because it has been supposed
that the 2p atomic obritals lie significantly higher in energy than
the 2s orbitals (Fig. 9C.4).
- These two 𝜎 orbitals formed from the 2p orbitals are labelled
2𝜎 and 2𝜎 , respectively.
- Note how the numbering follows the the order of increasing
energy and orbitals of different sysmetry
are labelled separately.
Antibonding 𝝈 orbital

Bonding 𝝈 orbital
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- Now consider the 2px and 2py orbitals of each atom.
- These orbitals are perpendicular to the internuclear axis and
may overlap laterally.
- This overlap may be constructive or destructive and results in
a bonding (𝜋 ) or an antibonding 𝜋 orbitals (𝜋 ) (Fig. 9C.5).
- Two neighbouring 2px orbitals overlap to give a bonding and
antibonding 𝜋 orbitals, and two 2py orbitals overlap to give
a bonding and antibonding 𝜋 orbitals.

Antibonding 𝝅 orbital Bonding 𝝅 orbital

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
- The 𝜋 and 𝜋 bonding orbitals are degenerate;
so their antibonding partners are also degenerate.
- We also see from Fig. 9C.5 that a bonding 𝜋 orbital (𝜋 ) has
has odd parity (𝑢) and an antibonding 𝜋 orbital (𝜋 ) has even
parity (𝑔).
- The lower two doubly degenerate orbitals are therefore labelled
1𝜋 and their higher energy antibonding partners are labelled
1𝜋 .

Antibonding 𝝅 orbital Bonding 𝝅 orbital

9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ 𝜎 Orbitals and 𝜋 orbitals (cont.)
When two 2pz orbitals along the internuclear axis overlap
☞ A bonding 𝜎 orbital : 𝜎
A antibonding 𝜎 orbital : 𝜎
Antibonding 𝝈 orbital
(odd parity : 𝒖 )

Bonding 𝝈 orbital
(even parity : 𝒈 )
When 2px & 2py orbitals perpendicular to the internuclear axis overlap
☞ A bonding 𝜋 orbital : 𝜋
A antibonding 𝜋 orbital : 𝜋

Antibonding 𝝅 orbital Bonding 𝝅 orbital

(even parity : 𝒈 ) (odd parity : 𝒖 )

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ The overlap integral 𝑆
- The lowering of energy that results from constructive interference
between neighbouring atomic orbitals correlates with the extent
of overalp of the orbitals.
- As explained in Topic 9B, the extent to which two atomic orbitals
on different atoms overlap is measured by the overlap integral 𝑺:
𝑆 𝜓 ∗ 𝜓 𝑑𝜏 Definition Overlap integral (9C.3)
- If the atomic orbital 𝜓 on 𝐴 is small and the orbital 𝜓 on 𝐵
is large, or vice versa, then the product of their amplitudes
is everywhere small and the integral (which is the sum of these
products) is also small (Fig. 9C.6).
- If 𝜓 and 𝜓 are both large in some region of space,
then 𝑆 may be large.

Small 𝑆
Large 𝑆
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ The overlap integral 𝑆 (cont.)
- If two normalized atomic orbitals are identical (for example,
1s orbitals on the same nucleus), then 𝑆 1.
- In some cases, simple formulas can be given for overlap integrals
(Table 9C.1) and illustrated in Fig. 9C.7.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ The overlap integral 𝑆 (cont.)
- Now consider the arrangement in which an s orbital is
superimposed on a px orbital of a different atom (Fig. 9C.8).
- The integral over the region where the product of orbitals is
positive exactly cancels the integral over the region where
the product of orbitals is negative, so overall 𝑆 0 exactly.
- Therefore, there is no net overlap between s and p orbitals
in this arrangement.
positive

No net overlap
negative
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ The overlap integral 𝑆 (cont.)
- The extent of overlap as measured by the overlap integral is
suggestive of the contribution that different kinds of orbital
overlap makes to bond formation, but the value of the integral
must be treated with caution.
- Thus, the overlap integral for broadside overlap of 2px, or 2py
orbitals is typically greater than that for the overlap of 2pz
orbitlas, suggesting weaker 𝜎 than 𝜋 bonding.
- However, the constructive overlap in the region between
the nuclei and on the axis is greater in 𝜎 interactions, and its
effect on bonding is more important than the overall extent of
overalp.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ The overlap integral 𝑆 (cont.)
- As a result, the separation of 1𝜋 and 1𝜋 orbitals is likely to be
smaller than the separation of 2𝜎 and 2𝜎 orbitals in the same
molecule.
- The relative energies of these orbitals are likely to be as shown in
Fig. 9C.9, and electrons occupying 𝜋 orbitals are likely to be less
effective at bonding than those occupying the 𝜎 orbitlas derived
from the same p orbitals.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ Period 2 diatomic molecules
- To construct the molecular orbital energy level diagram
for Period 2 homonuclear diatomic molecules (only 2s and 2p
atomic orbitals are considered), we form eight molecular orbitals
from the eight valence shell orbitals (four from each atom).
- In some cases, 𝜋 orbitals are less strongly bonding than
𝜎 orbitals because their maximum overlap occurs off-axis.
- This relative weakness of 𝜋 orbitals suggests that the molecular
orbital energy level diagram becomes as shown in Fig. 9C.10.

Molecular orbital energy level diagram

for O2 and F2.

9C. MO theory: homonuclear diatomic

□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- However, we must remember that
☞ we have assumed that 2s and 2pz orbitals contribute to
different sets of molecular orbitals whereas in fact all four
atomic orbitals(2s,2pz for A & 2s,2pz for B) have the same symmetry
around internuclear axis and contribute jointly to four 𝜎 orbitals.
- Thus, there is no guarantee that this order of energies (1𝜎 … 2𝜎 )
should prevail, and it is found experimentally (by spectroscopy)
and by detailed calculation that the order varies along Period 2
(Fig. 9C.11).

The order of energies

for 2𝜎 and 1𝜋 varies
between N2 and O2.
9C. MO theory: homonuclear diatomic
□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- The order shown in Fig. 9C.12 is appropriate as far as N2,
and Fig. 9C.10 is appropriate for O2 and F2.
- Relative order is controlled by the separation of 2s & 2p orbitals
in atoms (Separation increases toward the right of periodic table).
- The consequent switch in order occurs at about N2.
Molecular orbital energy level diagram For O2 and F2.
for diatomics up to N2.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- With the molecular orbital energy level diagram established,
we can deduce the probable ground configurations of
the molecules by adding the appropriate number of electrons
to the orbitals and following the building-up rules.
- Anionic species (such as the peroxide ion, O22-) need
more electrons than the parent neutral molecules (O2);
↔ Cationic species (such as O22+) need fewer electrons.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- Consider N2, which has 10 valence electrons.
① Two electrons pair, occupy and fill the 1𝜎 orbital.
② The next two occupy and fill the 1𝜎 orbital.
③ Six electrons remain.
 There are two 1𝜋 orbitals,
so four electrons can be
accommodated in them.
 The last two enter the 2𝜎 orbital.
☞ Thus, the ground-state configuration of N2 is 1𝜎 1𝜎 1𝜋 2𝜎 .
∗
- It is sometimes helpful to include an to denote
an antibonding orbital, in which this configuration would be
denoted 1𝜎 1𝜎 ∗ 1𝜋 2𝜎 .

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- A measure of the net bonding in a diatomic molecule is
its bond order 𝑏:
𝑏 𝑁 𝑁∗ Definition Bond order (9C.4)
where 𝑁 is the number of electrons in bonding orbitals and
𝑁 ∗ is the number of electrons in antibonding orbitals.
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
Brief illustration 9C.1 - Bond order

𝑏 𝑁 𝑁∗
- Each electron pair in a bonding orbital increases the bond order by 1
and each pair in an antibonding orbital decreases 𝑏 by 1.
① For H2, 𝑏 1 (one bonding orbital in 1𝜎 ), corresponding to
a single bond, H-H, between the two atoms.
② In He2, 𝑏 0 (one bond and one antibond in 1𝜎 1𝜎 ∗ ),
and there is no bond.
③ In N2, 𝑏 8 2 3 (four bonds and one antibond in 1𝜎 1𝜎 ∗ 1𝜋 2𝜎 ).
This bond order corresponds to Lewis structure of the molecule (:N≡N:).

9C. MO theory: homonuclear diatomic

□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- The ground-state electron configuration of O2 with 12 valence
electrons is 1𝜎 1𝜎 2𝜎 1𝜋 1𝜋 (1𝜎 1𝜎 ∗ 2𝜎 1𝜋 1𝜋 ∗ ).
- Its bond order is 2. ※ 𝑏 1/2 𝑁 𝑁 ∗ 1/2 8 4
- However, according to the building-up principle, two 1𝜋
electrons occupy different orbitals:
 One will enter 1𝜋 , and the other will enter 1𝜋 , .
∴ Ground-state configuration of O2 is 1𝜎 1𝜎 2𝜎 1𝜋 1𝜋 , 1𝜋 ,
- Because the electrons are in different orbitals, they will have
parallel spins.
- Thus, we can predict that an O2 molecule will have a net spin
angular momentum 𝑆 1 (∵ these electrons have 𝑠 1/2) and
be in a triplet state (∵ 2𝑆 1) as introduced in Topic 8C.
- As electron spin is the source of a magnetic moment,
we can predict that O2 should be paramagnetic (Topic 18C).
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- An F2 molecule has two more electrons than an O2 molecule.
- Therefore, its configuration is 1𝜎 1𝜎 ∗ 2𝜎 1𝜋 1𝜋 ∗ and 𝑏 1.
- We conclude that F2 is a singly-bonded molecule,
in agreement with its Lewis structure.
- The hypothetical molecule Ne2 has two additional electrons:
 Its configuration is 1𝜎 1𝜎 ∗ 2𝜎 1𝜋 1𝜋 ∗ 2𝜎 ∗ and 𝑏 0.
- Zero bond order is consistent with the monatomic nature of Ne.

- Bond order is a useful parameter for discussing the characteristics

of bonds because it correlates with bond length & bond strength.
The greater the bond order, the shorter the bond.
The greater the bond order, the greater the bond strength.
Physical interpretation

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
- Table 9C.2 lists some typical bond lengths in diatomic and
polyatomic molecules.
- The strength of a bond is measured by its bond dissociation
energy ℎ𝑐𝐷 (which is that the energy required to separate
the atoms to infinity) or by the well depth ℎ𝑐𝐷 with ℎ𝑐𝐷
ℎ𝑐𝐷 ℏ𝜔. ※𝐸 ℏ𝜔 : Zero-point energy for Harmonic oscillator
- Table 9C.3 lists some experimental values of ℎ𝑐𝐷 .

The greater the bond order, The greater the bond order,
the shorter the bond. the greater the bond strength
9C. MO theory: homonuclear diatomic molecules (cont.)
□ Electron configurations (cont.)
○ Period 2 diatomic molecules (cont.)
Brief illustration 9C.2 - Judging the relative bond strengths of molecule and ion
Predict whether N2+ has a larger or smaller dissociation energy than N2.

Method) Because the molecule with the higher bond order is likely to have
the higher dissociation energy, compare their electronic configurations
and assess their bond orders.

Sol) - From Fig. 9C.12, the electron configurations

and bond orders are
N2 1𝜎 1𝜎 ∗ 1𝜋 2𝜎 𝑏 3
N2+ 1𝜎 1𝜎 ∗ 1𝜋 2𝜎  𝑏 2.5
- Because the cation (N2+) has the smaller bond order,
we expect it to have the smaller dissociation energy.
- The experimental dissociation energies are 945 𝑘𝐽/𝑚𝑜𝑙 for N2
and 842 𝑘𝐽/𝑚𝑜𝑙 for N2+.

9C. MO theory: homonuclear diatomic molecules (cont.)

□ Photoelectron spectroscopy
○ Photoelectron spectroscopy
- We studied molecular orbitals as purely theoretical constructs,
but is there experimental evidence for their existence?
- Photoelectron spectroscopy (PES) measures the ionization
energies of molecules when electrons are ejected from different
orbitals by absorption of a photon of known energy, and
uses the information to infer the energies of molecular orbitals.
- The technique is also used to study solids & surfaces.
① UPS (ultraviolet photoelectron spectroscopy)
: It is used to study the electronic structure of valence electrons.
② XPS (X-ray photoelectron spectroscopy)
: It is used to study the electronic structure of core electrons.