Molecular Shape and Structure.

Lewis Model (Localized electron model).

The Valence-Shell Electron-Pair

Repulsion (VSEPR) Model
Electrostatic interactions between pairs of e-s.

Valence Bond Theory Molecular Orbital Theory

Describe the distribution of e-s and molecular shape in terms of the
occupation of orbitals.

Covalent Bond formation

Molecular Orbital Theory (MOT)

Molecular orbital theory has

proved to be the most successful
theory of the chemical bond: it
overcomes all the deficiencies of
Lewis’s theory and is easier to Friedrich Hund Robert Mulliken
use in calculations than valence- (1896-1997) (1896-1986)
Nobel Prize for chemistry
bond theory. in 1966.

Both introduced the TOM in the

late 1920s.
The Limitations of Lewis’s Theory
Lewis and VB Theory sometimes leads to an incorrect electronic description.

Paramagnetic properties of O2 Electron-deficient compound

Molecular Orbital Theory (MOT)

Paramagnetic properties of O2

A diamagnetic substance is one that tends to move out of a magnetic field

and a paramagnetic substance is one that tends to move into a magnetic
field.

Acording to Lewis and VBT:

Diamagnetic

However, experimentally:
Molecular Orbital Theory (MOT)
Electron-deficient compound
Electron-deficient compound is a compound with too few valence
electrons to be assigned a valid Lewis structure.
B2H6, diborane: a colorless gas that bursts into flame on contact with
air.
12 valence electrons
To the Lewis structure, it needs at least seven bonds, and therefore 14
electrons, to bind the eight atoms together!

VBT: resonance hybrid of the two structures

But the explanation is not straightforward.
Molecular Orbital Theory (MOT)

Unlike Lewis’s theory, molecular orbital theory can account for the
paramagnetism of oxygen and the existence of electron-deficient
compounds.
In MOT, electrons occupy orbitals called molecular orbitals that spread
throughout the entire molecule.
In MOT all valence electrons are delocalized over the whole molecule, not
confined to individual bonds.

linear combination of atomic orbitals

(LCAO)
A B YA1s is a 1s-orbital centered on one atom (A)
YB1s is a 1s-orbital centered on the other atom (B).

Any molecular orbital formed from a linear combination of atomic orbitals

on different atoms is called an LCAO-MO.
Molecular Orbitals (MO): space and pictured in three dimensions.
Molecular Orbital Theory (MOT)
Hydrogen molecule (H2(g))

linear combination of atomic orbitals

(LCAO-MO)
A B YA1s is a 1s-orbital centered on one atom (A)
YB1s is a 1s-orbital centered on the other atom (B).
Region of enhanced amplitude Region of diminished amplitude

Wavefunctions
of each atom

Two 1s-orbitals overlap in the same Two 1s-orbitals overlap in the same
region of space, and the wavefunctions region of space, and the
have the same signs in that region. wavefunctions have opposite signs.
CONSTRUCTIVE INTERFERENCE DESTRUCTIVE INTERFERENCE
BONDING MOLECULAR ORBITAL ANTIBONDING MOLECULAR ORBITAL
Molecular Orbital Theory (MOT)
Electron Configurations of Diatomic Molecules. Hydrogen molecule (H2(g))
Molecular Orbital Energy-level Diagram

An antibonding molecular orbital

has higher energy and lower
stability than the atomic orbitals
from which it was formed.

A bonding molecular orbital has

lower energy and greater stability
than the atomic orbitals from which
it was formed.
 Molecular Orbital Theory (MOT) Hydrogen molecule (H2(g))
As the names “bonding” and “antibonding” suggest, placing electrons in a
bonding molecular orbital yields a stable covalent bond, whereas placing
electrons in an antibonding molecular orbital results in an unstable bond.

N molecular orbitals can be constructed from N atomic orbitals.

The net number of bonds,

allowing for the cancellation
of bonds by antibonds
Valence Bond Theory (VBT)

+ -
- +
- +
>
<
+
+

+
+

+
+

+
+

10
=

11
Molecular Orbital Theory (MOT)

Electron Configurations of Diatomic Molecules.

Homonuclear diatomic molecules of Period 2 elements

Li2, Be2, B2, C2, N2, O2 and F2 molecules

First build all possible molecular orbitals from the available
valence-shell atomic orbitals. Then accommodate the
valence electrons in molecular orbitals by using the same
procedure used in the building-up principle for atoms

The ground-state electron configurations of diatomic molecules are deduced by

forming molecular orbitals from all the valence-shell atomic orbitals of the two
atoms and adding the valence electrons to the molecular orbitals in order of
increasing energy, in accord with the building-up principle.
 Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements
Li2, Be2, B2, C2, N2, O2 and F2 molecules
Period 2 atoms have 2s- and 2p- orbitals in their valence shells, forming
molecular orbitals from the overlap of these atomic orbitals. There are a
total of 8 atomic orbitals; so we can expect to build 8 molecular orbitals.
Nodes Nodes

Two p-orbitals can

overlap side by side to
give bonding and
antibonding π-orbitals.

Two p-orbitals can overlap to give

bonding and antibonding
σ-orbitals.
Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements

Li2, Be2, B2, C2 and N2 molecules O2 and F2 molecules

Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements

N2

Bilding Molecular Orbitals Filling Molecular Orbitals

Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements
N2 Filling Molecular Orbitals

Bilding Molecular Orbitals

σ2s 2σ*2s2π2p 4σ2p 2

N2 effectively has three bonds between the N atoms, just as the Lewis structure suggests.
Molecular Orbital Theory (MOT)

Homonuclear diatomic molecules of Period 2 elements

O2

Bilding Molecular Orbitals Filling Molecular Orbitals

Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements
O2

σ2s 2σ*2s2σ2p 2π2p 4π*2p1π*2p1

O2 has two unpaired electrons in the degenerate π*2p orbitals, so it is paramagnetic.
Molecular Orbital Theory (MOT)

Homonuclear diatomic molecules of Period 2 elements

F2

Bilding Molecular Orbitals Filling Molecular Orbitals

Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements
F2

σ2s 2σ*2s2σ2p 2π2p 4π*2p4

F2 is a singly bonded molecule, in agreement with the Lewis structure.
Molecular Orbital Theory (MOT)
Homonuclear diatomic molecules of Period 2 elements

Bond order
Bond length (pm)
Bond Enthalpy
(kJ/mol)
Molecular Orbital Theory (MOT)

Molecular orbitals are built from linear combinations of atomic orbitals:

when atomic orbitals interfere constructively, they give rise to bonding
orbitals; when they interfere destructively, they give rise to antibonding
orbitals. N atomic orbitals combine to give N molecular orbitals.

 MOT explains why the electron pair is so important for bond

formation and predicts that oxygen is paramagnetic.
 MOT accommodates electron-deficient compounds such as the
boranes just as naturally as it deals with methane and water.
 MOT can be extended to account for the structures and properties of
metals and semiconductors.
 MOT can also be used to account for the electronic spectra of
molecules, which arise when an electron makes a transition from an
occupied molecular orbital to a vacant molecular orbital.
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
To homonuclear diatomic molecules, LCMO:

coefficients cA and cB are not equal.

The relative values of cA2 and cB2 determine the type of bond:
• In a nonpolar covalent bond, cA2=cB2 and the electron pair is shared equally
between the two atoms.
• In an ionic bond, the coefficient belonging to one ion is nearly zero because the
other ion captures almost all the electron density.
• In a polar covalent bond, the atomic orbital belonging to the more
electronegative atom has the lower energy, and so it makes the larger
contribution to the lowest energy molecular orbital. Conversely, the contribution
to the highest-energy (most antibonding) orbital is greater for the higher-energy
atomic orbital, which belongs to the less electronegative atom.
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
To homonuclear diatomic molecules, LCMO:

coefficients cA and cB are not equal.

The relative values of cA2 and cB2 determine the type of bond:
• In a nonpolar covalent bond, cA2=cB2 and the electron pair is shared equally
between the two atoms.
• In an ionic bond, the coefficient belonging to one ion is nearly zero because the
other ion captures almost all the electron density.
• In a polar covalent bond, the atomic orbital belonging to the more
electronegative atom has the lower energy, and so it makes the larger
contribution to the lowest energy molecular orbital. Conversely, the contribution
to the highest-energy (most antibonding) orbital is greater for the higher-energy
atomic orbital, which belongs to the less electronegative atom.
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
A typical smolecular orbital energy level diagram for a heteronuclear
diatomic molecule AB.

Less electronegative, higher energy,

larger contribution to the
antibonding MO (s* )

More electronegative, lower energy,

and larger contribution to the
bonding MO (s)

When the atoms are close to one another in a row of the periodic table, the MO have
the same relative order of energies as those for homonuclear diatomic molecules.
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
The MO are labeled by using two different standard conventions.
σ∗2p≡ 4σ∗
The MO schemes typical of those calculated for
a diatomic oxide molecule, EO (where E= C for
π∗2p≡ 2π∗ CO and E=N for NO).

The MO energy-level diagrams of

σ2p≡ 3σ heteronuclear diatomic molecules are
much harder to predict qualitatively and
π2p≡ 1π we have to calculate each one explicitly
because the AO´s contribute differently to
each one.

σ∗2s≡ 2σ∗
Example:
σ2s≡ 1σ
NO
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
Ground-state electron configurations of heteronuclear diatomic molecules.

σ∗2p≡ 4σ∗

Ν Οσ2s: 2 σ*2s2 π2p 4 σ2p 2 π*2p1

N2p
π∗2p≡ 2π∗
Ν Ο σ: 12 2σ*1 π 43 σ2 2π*1

σ2p≡ 3σ Paramagnetic molecule

π2p≡ 1π

N2s
Lewis structure
σ∗2s≡ 2σ∗

σ2s≡ 1σ
N O
NO
Molecular Orbital Theory (MOT)
Heteronuclear Diatomic Molecules
Ground-state electron configurations of heteronuclear diatomic molecules.

σ∗2p≡ 4σ∗ CO, carbon monoxide molecule

CO: σ2s 2 σ*2s2 π2p 4 σ2p 2

C2p2
π∗2p≡ 2π∗
CO : 1σ 2 2σ*1 π 43 σ 2
O2p4 Bond order=3
σ2p≡ 3σ

π2p≡ 1π Lewis structure

C2s2
Diamagnetic molecule
σ∗2s≡ 2σ∗
O2s2
If the two atoms differ appreciably, you can no
σ2s≡ 1σ
longer use the scheme appropriate for
C O homonuclear diatomic molecules. Example: HF
CO
CHAPTER 5: COVALENT BOND

Ionic vs covalent bonds

Ionic vs covalent bonds
Ionic and covalent bonding are two extreme models of the chemical bond.
Most actual bonds lie somewhere between purely ionic and purely covalent.

Bonds between Bonds between

metal and nonmetal nonmetals

Ionic bonding Covalent bonding

However, the bonds in many compounds seem to have properties between the
two extreme models of bonding.

Can we describe these bonds more accurately by improving the two basic
models?
 Ionic vs covalent bonds
Correcting the Covalent Model: Electronegativity
Resonance hybrids of purely covalent and purely ionic structures.

Nonpolar covalent bond

Predominant structure, Small contribution, same energy,
bond almost purely covalent the average charge on each atom is zero

Unequal contributions, highlighting structure

has lower energy. Development of partial charges.
δ+ δ-

Polar covalent bond

All bonds between atoms of different elements (different electronegativities) are

polar to some extent.
 Ionic vs covalent bonds
Correcting the Covalent Model: Electronegativity

Polar covalent bond

Unequal contributions, highlighting structure

has lower energy. Development of partial charges.

δ+ δ- Electric dipole moment, m: size of electric dipole. Is a

measure of the magnitude of the partial charges and
their separation.

µHCl=1.1D This value are related with a partial charge of about 23% of an
electron’s charge on the Cl atom and an equivalent positive charge on the H atom

When the two atoms in a bond have only a small electronegativity

difference, the partial charges are very small. As the difference in
electronegativities increases, so do the partial charges, and the ionic
character of the covalent bond.
Ionic vs covalent bonds
Correcting the Covalent Model: Electronegativity

Dependence of the percentage

ionic character of the bond on the
difference in electronegativity, Dc,
between two bonded atoms for a
number of halides.
Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability

All ionic bonds have some covalent character.

The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.

Atoms and ions that readily undergo a

large distortion are said to be highly
polarizable.

Atoms and ions that can cause large

distortions are said to have a high
polarizing power.
Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability

All ionic bonds have some covalent character.

The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.

Atoms and ions that readily undergo a

large distortion are said to be highly
polarizable.

Atoms and ions that can cause large

distortions are said to have a high
polarizing power.
Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability

All ionic bonds have some covalent character.

The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.
Atoms and ions that readily undergo
a large distortion are said to be highly
polarizable.

Large Anions : highly polarizable.

Cations:
Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability

All ionic bonds have some covalent character.

The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.
Atoms and ions that readily undergo
a large distortion are said to be highly
polarizable.

Large Anions : highly polarizable.

Cations are not significantly polarizable

because the remaining electrons are held
so tightly.
Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability

All ionic bonds have some covalent character.

The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.

Atoms and ions that readily undergo a

large distortion are said to be highly
polarizable.

Atoms and ions that can cause large

distortions are said to have a high
polarizing power.
 Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability
All ionic bonds have some covalent character.
The spherical electron cloud of the anion becomes distorted in the direction of
the cation.
Ionic bonds acquire more covalent character as the distortion of the electron
cloud on the anion increases.
Atoms and ions that can cause large
distortions are said to have a high
polarizing power.

Small and highly charged Cations : strong

polarizing power.

Compounds composed of a small, highly charged cation and a large, polarizable

anion tend to have bonds with considerable covalent character.
 Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability
All ionic bonds have some covalent character.
Compounds composed of highly polarizing cations and highly
polarizable anions have significant covalent character in their bonding.
Polarizability
Anions become larger, and hence
more strongly polarizable, from right
to left across a period.

Anions become larger and hence more

Polarizability

strongly polarizable down a group.

 Ionic vs covalent bonds
Correcting the Ionic Model: Polarizability
All ionic bonds have some covalent character.
Compounds composed of highly polarizing cations and highly
polarizable anions have significant covalent character in their bonding.
- Polarizing power +
Cations become smaller, more highly
+

charged, and hence more strongly polarizing,

from left to right across a period.
Polarizing power

Cations become larger and hence less

strongly polarizing down a group.
-