Molecular Orbital (MO) Theory

Molecular Orbital Theory was primarily developed by Robert S. Mulliken and Friedrich Hund
in the early 20th century. This theory explains chemical bonding by treating molecules as a
single entity with electrons occupying molecular orbitals (MOs). The key principles discussed in
this theory include:

 The formation of molecular orbitals from atomic orbitals.

 The concepts of bond order and bond strength.
 The prediction of magnetic properties of molecules.

Postulates of Molecular Orbital Theory

1. Molecular Orbital Formation: When atomic orbitals (AOs) combine, they form new orbitals
called molecular orbitals (MOs). The electrons in these new orbitals are under the influence of
two or more nuclei, no longer belonging to a single atom.
2. Conservation of Orbitals: The total number of MOs formed is always equal to the total number
of AOs that combine.
3. Linear Combination of Atomic Orbitals (LCAO): This is the most common method for
approximating MOs. It involves either the addition or subtraction of the wave functions of the
combining AOs.
o Bonding Molecular Orbitals (BMOs): Formed by the additive overlap of wave functions
(ψBMO=ψA+ψB). They have lower energy than the parent AOs, and an increased electron density
between the nuclei, which leads to a stable bond.
o Antibonding Molecular Orbitals (ABMOs): Formed by the subtractive overlap of wave
functions (ψABMO=ψA+ψB). They have higher energy than the parent AOs, and a node (region of
zero electron density) between the nuclei, which destabilizes the bond.

o Non-bonding Molecular Orbitals: Formed when AOs cannot effectively overlap due to
symmetry or energy mismatch. These orbitals have the same energy as the parent AOs and do
not contribute to the bond.
4. Filling of Molecular Orbitals: Electrons fill the MOs according to the following rules:
o Aufbau Principle: MOs are filled in order of increasing energy.
o Pauli Exclusion Principle: Each MO can hold a maximum of two electrons with opposite spins.
o Hund's Rule: In degenerate orbitals (orbitals of equal energy), electrons are placed singly with
parallel spins before any pairing occurs.
Conditions for Linear Combination of Atomic Orbitals (LCAO)

For AOs to combine effectively and form stable MOs, they must satisfy three crucial conditions:

1. Comparable Energy: The combining AOs must have similar energies. For example, a 1s
orbital of one atom can combine with a 1s orbital of another, but a 1s orbital will not
effectively combine with a 2p orbital because of the large energy difference.
2. Proper Symmetry: The AOs must have the correct symmetry with respect to the
molecular axis. For instance, a pz orbital can only combine with another pz orbital, not a
px or py orbital, to form a sigma (σ) bond.

3. Effective Overlap: The AOs must overlap to a significant extent. Greater overlap leads
to a stronger bond and a more stable MO.

Characteristics of Bonding Molecular Orbitals (BMOs)

These orbitals promote chemical bonding and are formed by the constructive interference
(additive combination) of atomic orbital wave functions.

 Energy: They have lower energy than the original atomic orbitals, which makes the
molecule more stable.
 Electron Density: There is a high electron density in the region between the nuclei,
which increases the attractive force between the positive nuclei and the negative
electrons, holding the atoms together.
 Stability: Electrons in BMOs stabilize the molecule.
 Notation: They are represented by symbols like σ (sigma), π (pi) and δ.

Characteristics of Antibonding Molecular Orbitals (ABMOs)

These orbitals oppose chemical bonding and are formed by the destructive interference
(subtractive combination) of atomic orbital wave functions.

 Energy: They have higher energy than the original atomic orbitals, which destabilizes
the molecule.
 Electron Density: There is a node, or a region of zero electron density, between the
nuclei. This exposes the nuclei to each other, leading to repulsive forces.
 Stability: Electrons in ABMOs destabilize the molecule.
  Notation: They are denoted by an asterisk (*), such as σ∗ , π∗, δ∗.

Characteristics of Non-bonding Molecular Orbitals

These orbitals are formed when atomic orbitals are unable to combine effectively due to a lack of
proper symmetry or significant energy difference.

 Energy: They have the same energy as the original atomic orbitals.
 Electron Density: The electron density is localized on a single atom, often as a lone
pair, and is not shared between the nuclei.
 Effect on Bonding: The occupancy of these orbitals by electrons does not affect the
bond order or the stability of the molecule.

Difference between Bonding and Antibonding Molecular Orbitals

The difference between bonding and antibonding molecular orbitals of the MOT Theory are as
follows –

Bonding Molecular Orbitals Anti-Bonding Molecular Orbitals

Molecular orbitals formed by the additive effect of Molecular orbitals formed by the subtractive effect
atomic orbitals are called bonding molecular of atomic orbitals are called anti-bonding
orbitals. ψ(MO) = ψ A+ ψB molecular orbitals. ψ *(MO) = ψ A - ψB
The probability of finding electrons is more in the The probability of finding electrons is less in
case of bonding molecular orbitals antibonding molecular orbitals.
These are formed through the combination of + These are formed by the overlap or combination of
and + and – with – part of the electron waves + with the – part.
The electron density in the internuclear region is The electron density in the internuclear region is
high. Therefore, the nuclei are shielded from each very low. The nuclei get directly exposed to each
other and hence there is less repulsion. other and are less shielded.
These molecular orbitals are represented These molecular orbitals are represented
by σ, π, δ. by σ∗ , π∗, δ∗.
These are highly stable These are less stable
BMO’s Possess less energy ABMO’s Possess High energy

Molecular Orbital Energy Level Diagram for O₂

The molecular orbital diagram is created by combining the valence atomic orbitals (2s and 2p) of
the two oxygen atoms. Each oxygen atom has an electron configuration of 1s²2s²2p⁴. The valence
electrons are in the 2s and 2p orbitals, so we consider a total of 12 valence electrons (6 from each
atom) to fill the molecular orbitals.
The energy ordering of the molecular orbitals for O₂ and other diatomic molecules of elements
with an atomic number greater than 7 is:

σ₂ₛ 2 < σ₂ₛ2 < σ₂ₚz2 < (π₂ₚₓ = π₂ₚᵧ)4 < (π₂ₚₓ = π₂ₚᵧ)*2 < σ₂ₚ*0
Electrons are filled into these orbitals following the Aufbau principle (lowest energy first),
Hund's rule (one electron per degenerate orbital before pairing), and the Pauli Exclusion
Principle (maximum of two electrons per orbital with opposite spins).

Electron Filling and Properties

1. Valence Electrons: Each oxygen atom contributes 6 valence electrons, for a total of 12
electrons in the molecule.
2. Filling the Orbitals:
o The σ₂ₛ and σ*₂ₛ orbitals are filled with a total of four electrons.
o The σ₂ₚ orbital is filled with two electrons.
o The degenerate π₂ₚₓ and π₂ₚᵧ orbitals are filled with a total of four electrons (two in
each).
o The degenerate π₂ₚₓ and π₂ₚᵧ antibonding orbitals receive the final two electrons.
According to Hund's rule, these two electrons occupy separate orbitals with
parallel spins.
3. Bond Order: The bond order is calculated as half the difference between the number of
electrons in bonding orbitals and antibonding orbitals.
o Bonding electrons (Nb) = 8 (2 in σ₂ₛ, 2 in σ₂ₚ, 4 in π₂ₚ)
o Antibonding electrons (Na) = 4 (2 in σ₂ₛ, 2 in π₂ₚ)
o Bond Order = (8 - 4) / 2 = 2. This indicates a double bond between the two
oxygen atoms.
4. Magnetic Properties: The presence of two unpaired electrons in the degenerate π*₂ₚ
orbitals means that the O₂ molecule is paramagnetic. This is a significant experimental
observation that molecular orbital theory correctly predicts, while the Lewis structure
fails to.
Molecular Orbital Energy Level Diagram for CO

CO is a heteronuclear diatomic molecule, meaning it is composed of two different atoms, in

this case, carbon and oxygen. The electronegativity difference between carbon and oxygen is a
crucial factor that affects the energy of the molecular orbitals. Oxygen is more electronegative
than carbon, so its atomic orbitals are at a lower energy level than the corresponding orbitals of
carbon.

The total number of valence electrons in a CO molecule is 10 (four from carbon and six from
oxygen). The molecular orbitals are filled according to the Aufbau principle, Hund's rule, and the
Pauli exclusion principle, starting from the lowest energy level. The general order of molecular
orbitals for CO is:

σ2s 2 <σ2s∗2 < (π2px =2py)4 <σ2pz 2 <(π2px =2py) ∗0 <σ2pz∗0

The s-p mixing phenomenon is observed in CO, similar to nitrogen (N2). This mixing causes the
σ2p and π2p orbitals to switch their relative energy order, with the σ2p orbital being higher in
energy than the π2p orbitals.

The resulting electron configuration for CO is: (σ2s)2(σ2s∗)2(π2p)4(σ2p)2

Bond Order and Magnetic Properties

 Bond Order: The bond order is calculated using the formula:

 Bond Order = 1/2(No. of bonding electrons)−(No. of antibonding electrons) For CO, the
number of electrons in bonding orbitals is 8 (σ2s, π2p, and σ2p), and the number of
electrons in antibonding orbitals is 2 (σ2s∗).

Bond Order = ½ (8−2) = 3 This indicates a triple bond between the carbon and oxygen
atoms, which explains why CO is a very stable molecule.

 Magnetic Properties: According to its molecular orbital diagram, all of the electrons in
CO are paired. Molecules with all paired electrons are diamagnetic, meaning they are
not attracted to a magnetic field and are in fact slightly repelled by it.

 Molecular Orbital Diagram for 1,3-Butadiene

In 1,3 Butadiene, four carbon atoms are present C1, C2, C3 and C4; all are involved in sp2 Hybridization
and 1,3-butadiene has a conjugated π system with four carbon atoms, which leads to the formation
of four pi molecular orbitals (π). These orbitals are formed from the combination of the four p-
atomic orbitals, and each can hold a maximum of two electrons. Butadiene has a total of four pi
electrons, two from each double bond.

According to Molecular orbital theory, all the four carbon atoms in 1,3 Butadiene involves in LCAO
approach and produces four energy levels ( ) with four Molecular
Orbitals and).

The four pi molecular orbitals are arranged by increasing energy and number of nodes. A node is
a region of zero electron density. The orbitals below the energy of the original atomic orbitals are
bonding, and those above are antibonding.

 π1 (Bonding): This is the lowest energy orbital with zero nodes. The p-orbitals are all in
phase, resulting in constructive overlap across all four carbon atoms.
  π2 (Bonding): This is the next lowest energy orbital with one node located in the middle
of the molecule, between carbons 2 and 3. There is a bonding interaction between C1-C2
and C3-C4, but an antibonding interaction between C2-C3.
 π3 (Antibonding): This orbital has two nodes and is destabilizing. It has bonding
interaction between C2-C3, but antibonding interactions between C1-C2 and C3-C4. It is
the Lowest Unoccupied Molecular Orbital (LUMO).
 π4 (Antibonding): This is the highest energy orbital with three nodes. The p-orbitals are
out of phase with each other, resulting in destructive overlap and a highly unstable
orbital.

The four pi electrons of 1,3-butadiene fill the two lowest-energy bonding orbitals, π1 and π2,
with two electrons each, following the Aufbau principle and Pauli exclusion principle. The
Highest Occupied Molecular Orbital (HOMO) is π2.

Hence, the molecular orbital electronic configuration is 

 Molecular Orbital Diagram for Benzene (C6H6)

Benzene (C6H6) is a planar, hexagonal molecule consisting of a ring of six carbon atoms, each bonded to
one hydrogen atom. A key feature of its structure is that all carbon-carbon bond lengths are equal and
intermediate in length between a single bond and a double bond, which contradicts the idea of having
distinct single and double bonds. This is due to the presence of delocalized pi electrons located in
stabilizing electron clouds above and below the plane of the ring.

Molecular Orbital Description

In benzene, all six carbon atoms are sp2 hybridized.

 Each carbon uses three of its four valence electrons to form covalent sigma (σ) bonds
with two adjacent carbon atoms and one hydrogen atom.
 The remaining unhybridized p-orbital on each of the six carbon atoms contains one
electron.
 These six p-orbitals are oriented perpendicularly to the plane of the ring. They overlap
sideways to create a continuous, cyclic system of six pi (π) molecular orbitals—three
bonding and three antibonding orbitals.

The plus (+) and minus (-) signs in these orbital diagrams do not represent electrostatic charge.
Instead, they refer to the phase of the wave function. When orbitals with like phases overlap, it
results in a bonding interaction and a common region of electron density.

The six pi electrons then occupy these molecular orbitals in pairs, filling the three lowest-energy
bonding molecular orbitals completely. This arrangement, with a fully occupied set of bonding
orbitals, is what gives benzene its exceptional stability and unique aromatic properties.
1. In benzene, six carbon atoms are present C1, C2, C3, C4, C5 and C6, according to molecular orbital
theory, all the six carbon atoms are involving in LCAO approach and produces six molecular orbitals
 and , in four energy levels and . Note: The
HOMO of benzene is lower in energy than the HOMO of cyclohexatriene.

2. In these,  and are bonding energy level with one bonding molecular orbital and two
degenerate bonding molecular orbitals respectively.

3. Similarly and  are anti-bonding energy level with two degenerate anti-bonding
molecular orbitals  and one anti-bonding molecular orbital  respectively.
4. The  and  molecular orbitals contain 1, 2, 3 and 4 nodes in their structure
respectively. Thus, the increasing order of energy levels is . Note: There is
no Non-Bonding Molecular Orbitals in Benzene.
5. In benzene, three double bonds and  electrons are present, according to Hund’s rule, all the 6
electrons will occupy these molecular orbitals with increasing order of energy.

6. Out of these six electrons, two electrons would occupy the lowest energy molecular orbital  in
first (one bonding molecular orbital ) with their spins paired. The remaining four electrons will
occupy the two degenerate bonding molecular orbitals,  with their spins paired in each. Thus,
molecular orbital electronic configuration, in its ground state is

Hydrogen Bonding

Hydrogen bonding is a special and strong type of intermolecular force. It is a dipole-dipole

interaction that occurs when a hydrogen atom, which is covalently bonded to a highly
electronegative atom (like fluorine, oxygen, or nitrogen), is attracted to another nearby
electronegative atom.

Example: Hydrogen Bonding in Water (H2O) In a water molecule, the shared electrons in the
O-H bond are pulled closer to the more electronegative oxygen atom. This creates a polar
covalent bond, where the oxygen atom develops a partial negative charge (δ−), and the
hydrogen atom develops a partial positive charge (δ+). This partial positive hydrogen is then
electrostatically attracted to the partial
negative oxygen atom of an adjacent
water molecule.

Conditions for Hydrogen Bonding

For hydrogen bonding to occur, two main conditions must be met:

1. A highly electronegative atom: The molecule must contain a hydrogen atom bonded to
a highly electronegative atom, typically F, O, or N. The higher the electronegativity, the
stronger the polarity and the resulting hydrogen bond.
2. Small size of the electronegative atom: The electronegative atom must be small. A
smaller size allows for closer proximity to the hydrogen atom, which increases the
electrostatic attraction and makes the bond stronger.

Types of Hydrogen Bonding

Hydrogen bonds are classified into two main types based on their location.

1. Intermolecular Hydrogen Bonding

This type of hydrogen bonding occurs between different molecules of the same or different
compounds. It is responsible for many of the unique properties of substances like water,
ammonia (NH3), and hydrogen fluoride (HF), as it causes the molecules to associate with each
other.

 Examples:
o Water (H2O): Hydrogen bonds form between the hydrogen atom of one water
molecule and the oxygen atom of another.
Hydrogen fluoride (HF)

o Ammonia (NH3): Hydrogen bonds form between the hydrogen atom of one
ammonia molecule and the nitrogen atom of another.

o Alcohols and Carboxylic Acids: These organic compounds, which contain O-H
bonds, also exhibit strong intermolecular hydrogen bonding.

Hydrogen Bonding in Alcohols

Hydrogen Bonding in Carboxylic Acid

2. Intramolecular Hydrogen Bonding

This type of hydrogen bonding occurs within a single molecule. It happens when a molecule
contains two groups in close proximity: one with a hydrogen atom bonded to an electronegative
atom and another with an electronegative atom that can accept the hydrogen bond. This typically
forms a stable five- or six-membered ring structure.

 Example: o-nitrophenol, where a hydrogen bond forms between the hydrogen on the -
OH group and the oxygen on the nearby nitro group.

Effects and Properties of Hydrogen Bonding

Hydrogen bonding has a profound impact on the physical and chemical properties of a substance.

 High Boiling and Melting Points: Compounds with hydrogen bonds have unusually
high melting and boiling points because extra energy is required to break these strong
intermolecular forces. This explains why water (H2O) is a liquid at room temperature
while similar molecules like hydrogen sulfide (H2S) are gases.
 Viscosity and Surface Tension: Hydrogen bonding causes molecules to stick together,
or associate, which increases the substance's viscosity (resistance to flow) and surface
tension.
 Solubility: Substances that can form hydrogen bonds with a solvent (like water) are often
soluble. For example, lower alcohols are very soluble in water because they can form
hydrogen bonds with water molecules.
 Low Density of Ice: In solid ice, hydrogen bonding creates an open, cage-like crystal
structure where molecules are not as closely packed as they are in liquid water. As a
result, ice is less dense than liquid water, which is why it floats.
 Biological Importance: Hydrogen bonding is crucial for life, as it determines the three-
dimensional structures of essential biological molecules like proteins and DNA.
 Bond Strength: The hydrogen bond is a relatively weak bond, much weaker than a
covalent bond but significantly stronger than a weak van der Waals force. Its strength
depends on the electronegativity of the atoms involved.