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CHEM F111 General Chemistry Lecture 11

Chemical Bonding – Molecular orbital theory
 Review of lecture 10

• Terms, levels and term symbols for electronic states of

atoms
• Hund’s rules
• Selection rules for electronic spectra of atoms

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Determining Ground term and level
alone (revision)

If one wants to obtain the term and level only for ground (or the
lowest) state, then the same can be obtained very easily without
calculating the other possible terms and levels.
To get the ground (or the lowest energy) term for a configuration,
arrange the electrons in the subshell with leading to maximum spin
multiplicity. Calculate the maximum value of ML that can be
possible for this configuration which will be same as the L for the
ground term.
The lowest level can be obtained using the Hund's third rule.
e.g. nitrogen: 1s22s22p3: ML=0 → L=0; S=3/2 → Term is 4S, level
is 4S3/2.

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Molecular Hamiltonian

2 M
^ ℏ 1 2
H =− ∑ ∇A Nuclear kinetic energy (Tn)
2 A=1 m A
2 N
ℏ 2
− ∑ ∇ i Electronic kinetic energy (Te)
2 me i=1
M −1 M 2
ZAZBe
+∑ ∑ Inter-Nuclear repulsion energy (Vnn)
A=1 B=A+1 4 π ε0|⃗ r A −⃗r B|
M N 2
ZAe
−∑ ∑ Electron-nuclear attraction energy (Vne)
A=1 i=1 4 π ε r
|⃗
0 i −⃗ r A|
N −1 N 2
e Inter-Electronic repulsion energy (Vee)
+∑ ∑
i=1 j=i+1 4 π ε0|⃗r i −⃗r j|

Schrödinger equation using this form of Hamiltonian is intractable

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Born-Oppenheimer approximation
(BOA)

Nuclei are much more massive than electrons. Electronic motions are
on much faster time scales as compared to the nuclear motions.
Electrons can adjust immediately to instantaneous changes in the
positions of nuclei.
The BOA says that the total molecular wavefunction can be
accurately expressed as nuclear wavefunction multiplied by electronic
wavefunction (almost multiplicatively separable).
Solve the electronic Schrödinger equation for a series of fixed
positions of the nuclei.
^ e ({⃗r n }) ψe ({⃗r e }, {⃗r n })=E e ({⃗r n }) ψe ({⃗r e }, {⃗r n })
H

^ e =T^ e + V^ ne + V^ ee +[ V^ nn ]
H

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Born-Oppenheimer approximation
(BOA)

The electronic energy or molecular potential energy Ee({rn}) is obtained for

various nuclear positions for each electronic state and appears as the
potential energy for the nuclear Hamiltonian. The nuclear Schrödinger
equation gives energy states corresponding to the translations, rotations and
vibrations in the molecule.

[ T^ n + E e ({⃗r n })] ψn ({⃗r n })= E n ψn ({⃗r n })

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Potential energy curve in a diatomic
molecule

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Molecular orbital theory
We follow approach similar to what we did for atoms.
For example, consider the H2+ molecule – it is the simplest single-electron
diatomic molecule.
The electronic Hamiltonian for a diatomic molecule can be written as
2 2 2
ℏ
2
Z e Z e Z Z e
H^ e =− ∇ 2− A − B + A B
2 me 4 π ε0 r A 4 π ε0 r B 4 π ε0 r AB
For H2+ molecule ion, ZA=ZB=1. =1 However, we will keep ZA and ZB arbitrary, so
that our treatment can be applied to any one-electron diatomic molecule. The rA
and rB, are the distances of the electron from the nuclei A and B, respectively,
whereas, rAB is the distance between the two nuclei (and is fixed under BOA).
In principle, it is possible to obtain exact solutions to the Schrödinger equation of
a one-electron diatomic molecule.

Being one-electron system, the Hamiltonian eigenfunctions, are one-electron

functions of the molecule, are referred to as molecular orbitals (MO)s.
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Molecular orbital theory
How about many-electron diatomic molecules?
2
ℏ 2 2
H^ e =− ( ∇ 1 + ∇ 2)
2 me
Z A e2 Z B e2 Z A e2 Z B e2
Hamiltonian for a − − − −
2e molecule 4 π ε0 r 1 A 4 π ε 0 r 1 B 4 π ε0 r 2 A 4 π ε0 r 2 B
2
e
2
Z Z e
+ + A B
4 π ε 0 r 12 4 π ε0 r AB
One can use orbital approximation and express the total wavefunction in terms of
the anti-symmetrized product of the molecular orbitals.
ψ(1,2 ,…)=ϕi (1)ϕ j (2)…×spin part
Where, the фk’s are the MOs. The spatial and spin parts are chosen carefully to
ensure anti-symmetry in the many-electron wavefunction.
What about polyatomic molecules? – Need to obtain MOs by solving
Schrödinger equation for one-electron system of each polyatomic protoype –
highly impractical approach
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Molecular orbital theory

We note that although exact solution to a single-electron molecule is

possible, the exactness is of no use for many-electron atoms, as the many-
electron wavefunction is always approximate – for example, orbital
approximation
Once the set of MOs is identified, the procedure of getting the approximate
wavefunction for many-electron molecules for any prototype of molecules is
similar to that for the many-electron atoms case.
Thus, it is useful to develop and approximate method for describing the
MOs.
The chemical bonding is based on the concept of atoms coming close to
each other and sharing the electrons to increase stability of the system.
Thus, it is a good idea (and, indeed, a good approximation) to express the
MOs in terms of linear combination atomic orbitals (LCAO).

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Molecular orbital theory
We will now fix the conventions for convenience in writing and interpreting the
expressions: Ψ will be used for wavefunctions of systems; ф will be used for
representing molecular orbitals (MOs); and χ will be used for representing atomic
orbitals.
To start with, we consider the example of H2+ molecule ion. For this one-electron
system, the wavefunction ΨH2+ is just a molecular orbital ф and can be expressed
in terms of the linear combination of the atomic orbitals , χA and χB, which are
the 1s orbitals of the participating hydrogen atoms, A and B, respectively. Using
N as normalization constant, we have
ψ H + ≡ϕ= N (c A χ A +c B χ B )= N (c A 1 s A + c B 1 s B )
2

Since the two hydrogen atoms and the corresponding 1s orbitals are identical, it is
easy to both would contribute equally to the total MO probability density. This
results in two possiblities in the coefficients, thereby resulting in two MOs (and
the the wavefunctions): +
ψ H + ≡ϕ1 ≡σ g = N g (χ A + χ B )= N g (1 s A +1 s B )
2

−
ψ H + ≡ϕ 2 ≡σ u= N u (χ A−χ B )=N u (1 s A−1 s B )
2

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Bonding and anti-bonding MOs

+
ψ H + ≡ϕ1 ≡σ g = N g (1 s A +1 s B )
2
ψ−H + ≡ϕ 2 ≡σ u= N u (1 s A−1 s B )
2

Bonding Anti-bonding

Variation of the molecular orbitals along the inter-nuclear axis:

Note increased electron density between nuclei in bonding case,
and the node midway between nuclei in anti-bonding case

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H2+ molecule: Simple LCAO-MOs

MO’s characterized by:

●
Bonding / Anti-bonding character – lowering or raising the energy
●
Component of electronic angular momentum along the axis passing through the
nuclei:
0 (for σ), ħ (for π), 2ħ (for δ) – number of nodal planes containing axis.
●
Transformation under inversion – symmetric (g), anti-symmetric (u)
(Hetero-nuclear diatomic molecules lack this symmetry element.)
In the above example of H2+ molecule, we obtain only σg and σu orbitals
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The σ-, π- and δ- orbitals (FYI)

In general, diatomic molecules

can have π- and δ-orbitals in
addition to the σ-orbitals.
In a σ-orbital, no nodal plane
contains the inter-nuclear axis.
In a π-orbital, there is one nodal
plane containing the inter-
nuclear axis.
In a δ-orbital, two nodal planes
contain the inter-nuclear axis.

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Simple MO picture of H2 molecule

Use the molecular orbitals of H2+, and use the aufbau principle to get the
electronic configuration:
● Place both the electrons in the bonding MO, ф .
1
● The electronic configuration would be σ 2.
g
●
The ground state wavefunction would be
g.s. 1
ψ H (1,2)= σ g (1)σ g (2)[α(1)β(2)−β(1)α(2)]
2
√2
This is in fair agreement with experiment

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Simple MO picture of H2 molecule

The ground state wavefunction of H2 molecule is

g.s. 1
ψ H (1,2)= σ g (1)σ g (2)[α(1)β(2)−β(1)α(2)]
2
√2
Now we expand the MOs in terms of linear combination of the atomic orbitals
and write the spatial part of the ground state wavefunction and rearrange to get
g.s.
ψ H (1,2)spatial =σ g (1)σ g (2)
2

2
= N g (1 s A +1 s B )(1)(1 s A +1 s B )(2)

2
= N g [1 s A (1)1 s B (2)+1 s B (1)1 s A (2)] Covalent interaction
2
+ N g [1 s A (1)1 s A (2)] Ionic interaction
2
+ N g [1 s B (1)1 s B (2)] Ionic interaction
Homework: Write the wavefunction for the doubly-excited state of H 2 molecule
(electronic configuration: σu2). Using σu=Nu(1sA –1sB), expand the spatial part,
rearrange and see what you get.
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Bonding, anti-bonding and non-bonding
MO's and bond-order

Bonding orbitals – atomic orbitals overlap constructively; Probability density

increases in the region between the two nuclei; energy lower than that of the
constituent atomic orbitals. No nodal plane between the two nuclei
(perpendicular to the internuclear axis) e.g. σg, πu, δg ,..., orbitals.
Anti-bonding orbitals – atomic orbitals overlap destructively; a nodal plane
bisecting the internuclear axis; energy greater than that of the constituent
atoms. e.g. σu, πg , δu ,..., orbitals. (Also denoted by σ*, π*, δ*, …)
Non-bonding orbitals – atomic orbitals that cannot mix because of
symmetric/energetic incompatabilities remain almost unaltered and are called
non-bonding orbitals.
Bond order (BO) = (Nbonding – Nanti-bonding)/2;
(Nbonding=no of electrons in bonding orbitals; Nanti-bonding= no of electrons in
antibonding orbitals)

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He2 molecule?

Bond order = 0
Calculate the bond order for the following molecules:
H2, H2+, H2–, He2+, He2–. (Homework)
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Period 2 homonuclear diatomics

By convention, the inter-nuclear axis lies on z-axis.

The K shell (core) orbitals do not participate in bonding – these orbitals are
non-bonding in nature
1σ and 1σ* from the 2s orbitals
2σ and 2σ* from the 2pz orbitals

The bonding σ orbitals are symmetric

wrt inversion, hence are represented as
σg.
The antibonding σ orbitals (the σ*
orbitals) are antisymmetric wrt
inversion, hence represented as σu.

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Period 2 homonuclear diatomics

The linear combinations of the two 2px (or the two 2py) orbitals
result in formation of π and π* orbitals.

The bonding π orbitals are antisymmetric wrt inversion, hence are

represented as πu.
The antibonding π orbitals (the π* orbitals) are symmetric wrt
inversion, hence represented as πg.
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Symmetry and overlap

Overlap decreases with increase in

internuclear distance

Incompatible
symmetry
arrangement

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Construction of MO's using LCAO

●
Use all the available valence orbitals from the atoms
●
Classify them according to σ/π symmetry.
●
From N atomic orbitals of σ symmetry, build the N
(bonding+anti-bonding) molecular orbitals of σ symmetry.
●
Similarly from M atomic orbitals of π symmetry, build the M
(bonding+antibonding) molecular orbitals of π symmetry
●
In general, the MO energy increases with increase in the number
of inter-nuclear nodes. (However, there are exceptions in the
ordering of the MO's based on energy)

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MO energy level diagram for N2 and
smaller diatomics

Electronic configuration:
(KK),1σg21σu21πu42σg2

Bond order = (8–2)/2=3

What would be the bond orders

of N2+ and N2– molecules?

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MO energy level diagram for O2 and
larger diatomics

Electronic configuration:
(KK),1σg21σu22σg21πu41πg2
Bond order = (8–4)/2=2
What would be the bond orders
of O2+ and O2– molecules?
Tutorial discussion: Electronic
configurations and bond-orders
of second row homonuclear
diatomics

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Period 2 homonuclear diatomics:
relative MO energies

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