8.

The Chemical Bond

8.1 Introduction
 There are two principal quantum mechanical theories of
molecular electronic structure.
1. Valence-bond theory: The starting point is the concept of the
shared electron pair.
Covalent bond (quantum mechanical description): An electron pair
shared between two neighbouring atoms.
Ionic bond: The cohesion arises from the Coulombic attraction
between ions of opposite charge
 It is a limiting case of a covalent bond between dissimilar atoms.

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 The Chemical Bond

The theory discusses

 how to write the wavefunction for electron pair, and
 how it may be extended to account for the structures of a wide
variety of molecules.
 The theory introduces the concepts of spin pairing, orbital overlap
 and  bonds, promotion and hybridization.
2. Molecular orbital theory: The concept of atomic orbital is
extended to that of molecular orbital, which is a wavefunction that
spreads over all the atoms in a molecule.
The Born-Oppenheimer approximation
 The simplest molecule (H2+) consists of three particles (two nuclei
and one electron).

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 The Chemical Bond

 The nuclei, being so much heavier than an electron, move

relatively slowly and may be treated as stationary while the
electrons move in their field.
 The Born-Oppenheimer approximation allows us to select an
internuclear separation in a diatomic molecule and then to solve
the Schrödinger equation for the electrons at that nuclear
separation.
 Choose different separations and repeat the calculation.
 Explore how the energy of the molecule varies with bond length
(and with angles for polyatomic molecules) and obtain a
molecular potential energy curve.
 Once the curve has been calculated or determined experimentally
we can identify

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 The Chemical Bond

 The equilibrium bond length,

at the minimum of the curve,
and
 The bond dissociation energy,
Do, which is closely related to
the depth, De, of the minimum
below the energy of the
infinitely widely separated and
stationary atoms.

Fig. A molecular potential energy curve. The

equilibrium bond length corresponds to the
energy minimum.

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 The Chemical Bond

8.2. Valence-bond theory

 It is the first quantum mechanical theory of bonding to be
developed.
In VB theory, a bond is regarded as forming when an electron in an
atomic orbital on one atom pairs its spin with that of an electron
in an atomic orbital on another atom.
8.2.1. Diatomic Molecules: Hydrogen Molecule: Heitler-London
Theory
 Since the hydrogen molecule is formed from a combination of
hydrogen atoms A and B, a first approximation to its electronic
wavefunction might be assigning electron 1 to atom A and
electron 2 to atom B.
We write the wavefunction as:
(𝑟1, 𝑟2) = 1s(𝑟1A)1s(𝑟2B)
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 The Chemical Bond

When the two atoms are close to each other, it is not possible to
know whether it is electron 1 that is on A or electron 2.
An equally valid description is therefore
(𝑟1, 𝑟2) = 1s(𝑟1B)1s(𝑟2A)
 When the two are equally probable, quantum mechanics
describes the true state of the system as a superposition of the
wavefunctions for each possibility
 A better description of the molecule than either wavefunction
alone is the linear combination:
(𝑟1, 𝑟2) = 1s(𝑟1𝐴)1s(𝑟2𝐵) ± 1s(𝑟1B)1s(𝑟2A)
 The combination with lower energy is the one with a + sign, so
Heitler and London suggested that the valence-bond
wavefunction of the H2 molecule is
 𝑟1, 𝑟2 = 1s 𝑟1𝐴 1s 𝑟2𝐵 + 1s(𝑟1B)1s(𝑟2A)
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 The Chemical Bond

 The formation of the bond in H2 can be pictured as due to the

high probability that the two electrons will be found between
the two nuclei and hence will bind them together.
 There is an enhancement in the value of the wave function in the
internuclear region
 The electron distribution described by the wavefunction is called a
 bond.
 It has cylindrical symmetry around the internuclear axis.
 The wavefunction can be formed only by a pair of electrons with
opposed spins.
8.2.2. Valence bond theory of -electron systems
 The VB description of H2 can be applied to other homonuclear
diatomic molecules.
E.g. N2
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 The Chemical Bond

To construct the valence bond description of N2, consider the

valence electron configuration of each atom, which is 2s22px1
2py12pz1.
 Take the z-axis to be the internuclear axis
 A  bond is formed by spin pairing between the two electrons in
the two 2pz orbitals.
 The remaining 2p orbitals cannot merge to give  bonds
 Instead, they merge to form two  bonds.
 A  bond arises from the spin pairing of electrons in two p orbitals
that approach side-by-side
 There are two  bonds in N2 one formed by spin pairing in two
neighbouring 2px orbitals and the other by spin pairing in two
neighbouring 2py orbitals.
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 The Chemical Bond

8.2.3. Polyatomic molecules

Each  bond is formed by the spin pairing of electrons in atomic
orbitals along the relevant internuclear axis.
 bonds are formed by pairing electrons that occupy atomic orbitals
of the appropriate symmetry.
 E.g.1. The VB description of H2O
The valence electron configuration of an O atom is 2s22px2;2py1
2pz1
The two unpaired electrons in the O 2p orbitals can each pair with
an electron in an H Is orbital, and each combination results in the
formation of a .
Because the 2py and 2pz orbitals lie at 90° to each other, the two 
bonds also lie at 90° to each other.
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 The Chemical Bond

We can predict, therefore, that H2O should be an angular molecule,

which it is.
 The theory predicts a bond angle of 90°, whereas the actual
bond angle is 104.5o.
 This is the deficiency of the valence bond theory.
E.g.2. The valence bond theory is unable to account for carbon’s
tetravalent.
The ground-state configuration of C is 2s22px12py1
 It suggests that a carbon atom should be capable of forming only
two bonds, not four.
The deficiency is overcomes by allowing for promotion, the
excitation of an electron to an orbital of higher energy.

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 The Chemical Bond

 In carbon, the promotion of a 2s electron to a 2p orbital leads to

the configuration 2s12px12py12pz1
 The four electrons may pair with four electrons in orbitals
provided by four other atoms (such as four H Is orbitals if the
molecule is CH4), and hence form four  bonds.
 The description of the bonding in CH4 (and other alkanes) is
incomplete because it implies the presence of three  bonds of
one type (formed from H Is and C 2p orbitals) and a fourth 
bond of a different character (formed from H Is and C 2s).
 The problem is overcome by realizing that each electron
occupies a hybrid orbital formed by interference between the C
2s and C 2p orbitals.

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 The Chemical Bond

The specific linear combinations that give rise to four equivalent

hybrid orbitals are
hI = s + Px + Py + pz h3 = s - Px + Py - pz
h2 = s - Px - Py + pz h4 = s + Px - Py - pz
 The angle between the axes of the hybrid orbitals is the
tetrahedral angle, 109.47°.
 Each hybrid is called an sp3 hybrid orbital.
 Hybridization can also be used to describe the structure of an
ethene molecule
 The s AO can form hybrids with two of the p AO's to give three sp2
hybrid orbitals, with one p-orbital remaining unhybridized.
 The two unhybridized p-orbitals form a -bond
Similarly, ethyne molecule can be described through sp hybridization
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 The Chemical Bond

8.3. Molecular Orbital Theory

8.3.1. The linear combination of atomic orbitals (LCAO) - Molecular
orbital approximation
 Each MO is constructed from a superposition of atomic orbitals
belonging to the atoms in the molecule.
 An approximate molecular orbital formed from a linear
combination of atomic orbitals is called a LCAO-MO.
 The size of the contribution of an orbital from a particular atom
indicates the probability that the electron will be found on that
atom.
 The actual shape of the molecular orbital (and indirectly its
energy) is a reflection of the extent to which the individual atomic
orbitals interfere with one another either constructively or
destructively.
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 The Chemical Bond
8.3.2. The Hydrogen Molecular Ion, H2+

The hamiltonian for the single electron in H2+ is

 In the expression for V, the first two terms in parentheses are the
attractive contribution from the interaction between the electron
and the nuclei; the remaining term is the repulsive interaction
between the nuclei.
The one-electron wavefunctions obtained by solving the Schrödinger
equation H = E are called molecular orbitals (MO). A molecular
orbital , through the value of 2, gives the distribution of the
electron in the molecule.
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 The Chemical Bond

 A molecular orbital is like an atomic orbital, but spreads

throughout the molecule.
 The Schrödinger equation can be solved analytically for H2+
(within the Born-Oppenheimer approximation), but the
wavefunctions are very complicated functions and can not be
extended to polyatomic systems.
 A simpler procedure is the LCAO.

Linear combinations of atomic orbitals

 If an electron can be found in an atomic orbital belonging to atom
A and also in an atomic orbital belonging to atom B, then the
overall wavefunction is a superposition of the two atomic orbitals:

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 The Chemical Bond

 = 𝑁 𝐴 + 𝐵
where for H2+, 𝐴 = 𝐻1sA 𝑑𝜏 and B = 𝐻1sB 𝑑𝜏
And N is a normalization constant.
Example: Normalize + = N(A+B)
Solution:

Where,

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 The Chemical Bond

a) Bonding orbitals

 The probability density corresponding to the real wavefunction +

is:

A2 = the probability density if the electron were confined to the

atomic orbital A.
B2 = the probability density if the electron were confined to the
atomic orbital B.
2AB = an extra contribution to the density - the overlap density
 It represents an enhancement of the probability of finding the
electron in the internuclear region.
 Enhancement can be traced to the constructive interference of
the two atomic orbitals:
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 The Chemical Bond
 Electrons accumulate in regions where atomic orbitals overlap and
interfere constructively.
 This puts the electron in a position where it interacts strongly with
both nuclei.
 Hence, the energy of the molecule is lower than that of the
separate atoms
 The  orbital is an example of a bonding orbital - an orbital which,
if occupied, helps to bind two atoms together.
 The label 1 implies it is the  orbital with the lowest energy
 An electron that occupies a  orbital is called a  electron
 For H2+, the configuration of the molecule is 11.

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 The Chemical Bond
 The energy E1 of the 1-orbital is

Where,

 1 has gerade symmetry and is denoted as g

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 The Chemical Bond

b) Antibonding orbitals
The linear combination - corresponds to a higher energy than that
of +.
 The probability density is

 The energy E2 of the 2-antibonding orbital is given by

 Antibonding orbitals are often labeled with an asterisk (*)

 The 2 orbital could also be denoted as 2*
 2 has ungerade symmetry and is denoted as u

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 The Chemical Bond

 An antibonding electron is excluded from the internuclear region,

and hence is distributed largely outside the bonding region.
 A bonding electron pulls two nuclei together, an antibonding
electron pulls the nuclei apart
8.3.3. Homonuclear diatomic molecules
1. The Hydrogen Molecule
 It forms only  orbitals
 To deduce the ground electronic configurations of H2 we use the
H2+ molecular orbitals.
 The general procedure is to construct molecular orbitals by
combining the available atomic orbitals.
 The electrons supplied by the atoms are then accommodated in
the orbitals so as to achieve the lowest overall energy subject to
the constraint of the Pauli exclusion principle
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 The Chemical Bond

 As in the case of atoms, if several degenerate molecular orbitals

are available, we add the electrons singly to each individual orbital
before doubly occupying anyone orbital.
 If electrons do occupy different degenerate orbitals, then a lower
energy is obtained if they do so with parallel spins (Hund's
maximum multiplicity rule) .
 In H2, each hydrogen atom contributes a 1s orbital as in H2+
 Hence, we can form the lg and lu orbitals
Note: From N atomic orbitals we can build N molecular orbitals.
 A general principle of molecular orbital theory is that all orbitals of
the appropriate symmetry contribute to a molecular orbital.
 There are two electrons to accommodate, and both can enter lg
by pairing their spins,
 The ground-state configuration is therefore lg2
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 The Chemical Bond

 The atoms are joined by a bond consisting of an electron pair in a

bonding  orbital.

Fig. A molecular orbital energy level diagram for orbitals

constructed from the overlap of H1s orbitals
2. Molecular Orbital Theory of π-electron Systems
 Consider a homonuclear diatomic molecule.
 In elementary treatments, only the orbitals of the valence shell are
used to form molecular orbitals
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 The Chemical Bond
 For molecules formed with atoms from Period 2 elements, only
the 2s and 2p atomic orbitals are considered.
 To build  orbitals, we form linear combinations of all atomic
orbitals that have cylindrical symmetry about the inter- nuclear
axis.
 These orbitals include the 2s orbitals on each atom and the 2pz
orbitals on the two atoms.
 Consider the 2px and 2py orbitals of each atom.
 These orbitals are perpendicular to the internuclear axis and may
overlap broadside-on.
 This overlap may be constructive or destructive, and results in a
bonding or an antibonding  orbital

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 The Chemical Bond
 The two 2px orbitals overlap to give a bonding and antibonding x
orbital, and the two 2py orbitals overlap to give two y orbitals.
 The x and y bonding orbitals are degenerate; so too are their
antibonding partners.
 A bonding  orbital has odd parity and is denoted u
 An antibonding  orbital has even parity, denoted g
 To construct the molecular orbital energy level diagram for Period
2 homonuclear diatomic molecules, we form eight molecular
orbitals from the eight valence shell orbitals (four from each
atom).
 The relative order is controlled by the separation of the 2s and 2p
orbitals in the atoms, which increases across the group.
 The consequent switch in order occurs at about N2.

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 The Chemical Bond

 With the orbitals established, we can deduce the ground

configurations of the molecules by adding the appropriate number
of electrons to the orbitals and following the building-up rules.
 Consider N2 , which has 10 valence electrons.

Ground-state configuration of N2:

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 The Chemical Bond

 Consider O2 or F2lectrons.

Ground-state configuration of:

O2:
F2:

Fig. The molecular orbital energy level diagram for homonuclear diatomic
molecules (For O2. F2) 27
 The Chemical Bond

Bond order (b): A measure of the net bonding in a diatomic molecule

Where,
n = the number of electrons in bonding orbitals and
n* = the number of electrons in antibonding orbitals.
 Each electron pair in a bonding orbital increases the bond order by
1 and each pair in an antibonding orbital decreases b by 1.
E.g. For H2 , b = 1, corresponding to a single bond, H-H.
For He2 , b = 0, and there is no bond.
For N2 , b = ½(8 - 2) = 3.
Note:
The greater the bond order,
1. the shorter the bond.
2. the greater the bond strength. 28
 The Chemical Bond

8.4. Comparison of MO and VB Theories

Similarity
1. Atomic or molecular orbitals cannot have more than two electrons.
2. The theories include the sharing of electrons by the nuclei.
3. The energy of overlapping orbitals must be comparable and there
must be similarities in their symmetry.

Difference
Valence bond theory Molecular orbital theory
Explains hybrid orbitals Explains bonding molecular orbital
and antibonding molecular orbitals
Resonance plays a role No place for resonance
No explanation of paramagnetic Explains paramagnetic character of
character of O2 O2

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