Molecular Orbitals

CHEM 3205

Assoc. Prof. Dr. Sharon E. Lazaro, RCh, AMRSC

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 Molecular Orbitals
• elements bond with each other when they are chemically combined

• Electrons in bonding molecular orbitals have a high probability of occupying

the space between the nuclei

• the electrostatic forces between the electrons and the two positive nuclei
hold the atoms together.

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 Molecular Orbitals
Valence bond theory
• formation of a molecule as arising from
bringing together complete atoms

• usually represented by Lewis structures

• Lewis structures give the connectivity of
an atom in a molecule, the bond order,
and the number of lone pairs, used to
determine the shape of the molecule

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Nonbonding Pairs and Bond
Angle

 Nonbonding pairs are physically

larger than bonding pairs.
 Therefore, their repulsions are
greater; this tends to decrease bond
angles in a molecule.
Factors that affect Bond
Lengths
Repulsion trend : lp-lp> lp-bp> bp- bp
1.) a.) Size of the central atom
-assuming same number of bp and lp
NH3 > PH3 > AsH3 > SbH3

Increasing size and lower electronegativity of the central atom permit

the bonding electron to be drawn out further, thus decreasing
repulsion between bonding pairs (smaller bond length)

Same geometry with the same number of lp and bp

Smaller atom = larger bond length
Larger atom = smaller bond length
Multiple bonding
b.) Bond length within the period

 ↑ electronegativity; ↓ bond distance

BL: dP-O > dS-O> dCl-O

BO : PO43- < SO42- <ClO4-

↓ FC, ↑BO as seen in the decrease in BL

↑BO due to ↑ dπ capability
(capable of expanded octet)
(enhanced by dπ – pπ interaction)
Factors that affect Bond
Lengths
2. Electronegativity of the substituent
e.g. NF3 < NH3
↑ electronegativity, ↑ tendency to attract all electrons in the bond, less
electron in the bp, less repulsion, ↓ BL.
- Electron density is drawn towards the more electronegative atom
- less bp – bp repulsion
- also seen in F2O < H2O

e.g. PF3 < PH3

(multiple bonding is expected for PF3 because of π –π interaction.
P is larger than H, capable of π interaction with F making the bp more in
electron cloud
For P-H, H do not have p electron for π –π interaction.
Pauli- Exclusion Principle and
the VSEPR Theory
1.) Rule of thumb: lp-lp> lp-bp> bp-bp repulsion
2.) Effect of the size of central atom
↑ size and lower electronegativity => decreasing repulsion between
bonding pairs, bond length ↓
3.) Substituent atoms with increased electronegativity  decreased
repulsion between bp, ↓ bond length

Changes in geometry affected by lp

 4 electron pairs – can give rise to different angles and geometries
 Tyrigonal bipyramid 2 e- pairs in the axial position and 3 e- pairs in
the equatorial
 Molecular Orbitals
Molecular orbital theory
• allocates electrons to molecular
orbitals (MOs) formed by the overlap
of atomic orbitals

• allowed if the symmetries of the

atomic orbitals are compatible with
one another
• efficient if the region of overlap
between the atomic orbitals is
significant
• efficient if the atomic orbitals are
close in energy
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 Conditions for bonding
• the symmetry of the orbitals must be such that regions with the same
ψ sign of overlap

• the atomic orbital energies must be similar

• the distance between the atoms must be short enough to provide

good overlap of the orbitals

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 Molecular orbitals from s orbitals

• Interaction of these orbitals yields

an ‘in phase’ and an ‘out of
phase’ combination

• in phase (σ) - bonding

• out of phase (σ*) - antibonding.

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bital_Theory/Pictorial_Molecular_Orbital_Theory
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 Molecular orbitals from s orbitals
σ (sigma)
• molecular orbital that is a bonding molecular orbital
• has a lower energy than the original atomic orbitals (combination
of atomic orbitals results in an increased concentration of
electrons between the two nuclei)

σ*
• An antibonding orbital at higher energy since this combination of
atomic orbitals results in a node with zero electron density
between the nuclei

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 Molecular orbitals from p orbitals

The formation of a σ bonding and antibonding orbital using p-orbitals

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bital_Theory/Pictorial_Molecular_Orbital_Theory
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 Conditions for bonding

The side on overlap of p orbitals to form pi bonding and antibonding orbitals.

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bital_Theory/Pictorial_Molecular_Orbital_Theory
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 Conditions for bonding

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Molecular orbitals from s orbitals

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 Molecular orbitals from p orbitals

(a) Formation of molecular orbitals. (b) Orbitals that do not form molecular orbitals
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Molecular orbitals from p orbitals

Energy-level diagram 29
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Sketch the overlap regions of the following combination of orbitals, all with collinear
z axes, and classify the interactions.
a) pz and dxz b) s and dz2 c)s and dyz

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Sketch the overlap regions of the following combination of orbitals, all with collinear
z axes, and classify the interactions.
a) pz and dxz b) s and dz2 c)s and dyz

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Sketch the overlap regions of the following combination of orbitals, all with collinear
z axes, and classify the interactions.
a) pz and dxz b) s and dz2 c)s and dyz

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Sketch the overlap regions of the following combination of orbitals, all with collinear
z axes, and classify the interactions.
a) pz and dxz b) s and dz2 c)s and dyz

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Energy and molecular orbital formation

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Molecular orbitals of the first 10 elements

Additional labels which

describe the orbitals:
• g (gerade) , orbitals
symmetric to inversion
• u (ungerade) , orbitals
antisymmetric to inversion
(signs change on inversion

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Molecular orbitals of the first 10 elements

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Molecular orbitals of the first 10 elements

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Bond order

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Molecular-Orbital Theory Also Applies to
Heteronuclear Diatomic Molecules
• the energies of the
bonding molecular orbitals are
more similar to those of
the atomic orbitals of B

• the electron density of bonding

electrons is likely to be closer
to the more electronegative
atom

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• the 11th electron must occupy
one of the degenerate π* orbitals
• predicted bond order for NO is
2.5
• electronic configuration is
(σ2s)2(σ⋆2s)2(π2pxy)4(σ2pz)2
(π2p⋆xy)1
• has a single electron in a
relatively high-energy molecular
orbital

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HF

An MO diagram for HF
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Nonbonding Molecular Orbitals in HF
• The overlap between the H 1s
orbital and the F 2s is symmetry
allowed but the two orbitals are
not close enough in energy

• only the F 2pz orbital has a

symmetry-allowed overlap

An MO diagram for
HF
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 Molecular Orbital Theory
Because the contributions are not equal, the MO diagram will be skewed.

MO diagram for HF There is a little bit of mixing

between the H 1s and the F 2s
orbital but it interacts mostly
with the 2pz.

F also has the 2px and 2py

orbitals that cannot interact
with the H 1s orbital because
they have the wrong
symmetry! If you try to combine
these orbitals with the 1s on H,
you will find that the overlap
integral, S, is equal to 0. Thus
these orbitals are exclusively
found on the F atom and are
called non-bonding.

The orbitals that are derived mostly from F are going to be closer to the
energies of the atomic orbitals of F and vice versa.
1. Draw the Lewis structure of CO
2. Show the MO diagram for CO
3. Calculate the bond order
4. Is the number of bonds indicated by the bond order similar to the number of
bonds drawn using VSEPR model?

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 CO
• The ground state configurations
for carbon and oxygen are [He]2s22p2
and [He]2s22p4 ,respectively.

Incomplete Lewis structure of CO • electronegativity difference

between the two elements is 0.8
indicative of a covalent compound

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 CO

Simplified MO diagram for carbon monoxide, CO 49

 CO

Two other features of note

are:
• the highest occupied molecular
orbital (HOMO) - weakly σ-
antibonding and of
predominately carbon character

• a degenerate pair of π* orbitals

make up the lowest unoccupied
molecular orbital (LUMO).

Simplified MO diagram for carbon monoxide, CO 50

LiF

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 Molecular Interactions
• electric dipole moment, μ

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 Molecular interactions
Dispersion forces arise from momentary fluctuations in electron density which
produce temporary dipole moments that, in turn, induce dipole moments in
neighboring species.

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 Hydrogen bond
• formed between a hydrogen atom attached to
an electronegative atom, and an
electronegative atom that possesses a lone pair
of electrons
• In a typical X-H⋅⋅⋅Y interaction, the X-H covalent
bond is slightly longer and weaker than a
comparable bond in the absence of hydrogen
• much stronger than dipole-dipole interactions
and dispersion forces
• can have a significant affect on physical
properties of compounds e.g. boiling and
melting points

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 Hydrogen bond

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 56

[Fe(qsal-l)2] OTs

 There are I⋅⋅⋅O halogen bonds (∆vdw = –0.648 Å) and hydrogen

bonds between the tosylate anion and the cations and water.