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Instant Notes in Physical Chemistry

Instant Notes in Physical Chemistry

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Published by: Diksha Behl on Dec 29, 2011
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Key Notes

Direct calculation of the molecular orbitals is possible only in the
case of H2

+

. For more complex molecules, a range of
approximations must be made in order to predict the nature of the
molecular orbitals. In all cases, it is necessary to assume that the
nuclei are stationary relative to the motion of the electrons. This
is known as the Born-Oppenheimer approximation, and allows
the internuclear geometry and motion to be treated completely
separately from that of the electrons.

In all cases other than that of H2

+

, the molecular orbitals may be
approximately derived from a linear combination of atomic
orbitals. The atomic wavefunctions are combined in a linear

combination to give a molecular orbital,

,

where cm is the mixing coefficient. cm may be varied for all the
atomic orbitals so as to minimize the energy of the resulting
molecular orbital. The variation principle states that the lowest
energy calculated orbital most accurately describes the actual
molecular wavefunction.

A molecular bonding orbital differs from the atomic orbitals from
which it is derived as it increases the probability of finding an
electron in the internuclear region. This reduces the free energy
of the electrons, and that of the molecule as a whole. Antibonding
molecular orbitals are derived by subtraction of one or more
atomic wavefunction from the others. The energy of the resulting
antibonding molecular orbital is greater than that of the atomic
orbitals, since a node in the internuclear electron density causes
an increase in the internuclear repulsion.

The stability of a molecule is heavily dependent upon the extent
to which the orbitals are allowed to overlap. The extent of the
orbital overlap is determined by the internuclear distance. At
relatively large separations, the energy decreases as the nuclei are
brought together, and the atomic orbital overlap increases,
whereas at low internuclear distances a repulsion term is
dominant. There is a point at which these two opposing effects
balance, and the molecule adopts its lowest free energy state. For
the antibonding orbital, there is a fully repulsive interaction
between the nuclei at any distance.

Related topics

ThewavenatureofmatterElementary valence theory (H1)

Related topics

Valence bond theory (H2)

Many-electron atoms (G6)

The Born-Oppenheimer approximation

In contrast to valence bond theory (see Topic H2), molecular orbital theory attempts to
describe the bonding orbitals in a molecule in their entirety, as opposed to focusing on the
creation of each bond individually. Just as the explicit calculation of atomic orbitals is
only possible for the hydrogen atom, direct calculation of the molecular orbitals is
possible only in the simplest possible molecule, H2

+

. Unlike atomic wavefunctions, the
molecular wavefunction must describe the relative motion of nuclei in addition to the
motion of the electrons. Primarily because of their relative masses, the electrons move
some 103

times faster than the nucleus, and the Born-Oppenheimer approximation
simplifies the calculation of molecular orbitals by assuming that the nuclei are stationary
relative to the motion of the electron. This approximation allows the internuclear
repulsion terms to be treated completely separately from the electrostatic behavior of the
electrons.

The potential energy of an electron in the electric field resulting from two protons is
readily calculated using:

where rH1 and rH2 are the distances of the electron from each proton. Incorporation of this
potential energy expression into the Schrödinger equation (see Topic G4) yields the exact
solutions for the hydrogen molecular ion. As with atomic orbitals, the impossibility of
calculating orbitals for systems with three or more bodies in relative motion makes
mathematical solutions for the molecular orbitals impossible. Molecular orbital theory
therefore makes the approximation that the molecular orbitals may be formed by the
linear combination of atomic orbitals (LCAO).

The LCAO approximation

The total wavefunction for a molecule is given by:

where ψn represents the wavefunction for each electron in the molecule.
Explicit calculations for the molecular orbitals H2

+

show that the lowest energy
solution of the Schrödinger equation is given by the addition of the two 1s orbitals. In all
other cases, it is necessary to make the approximation that molecular orbitals may be
calculated from a linear combination of atomic orbitals. This linear combination
generates molecular orbitals by direct addition of atomic orbitals on the bonding atoms.

Physical chemistry 272

The wavefunctions for two electrons, ψ(A) and ψ(B), in the atomic orbitals on two atoms,
A and B respectively, are combined to form a molecular orbital. The molecular orbital
wavefunction is given by:

where cm is a mixing coefficient, which is calculated for each orbital so as to minimize
the molecular energy as calculated using the Schrödinger equation. It is a further

requirement that the mixing coefficients should be normalized, so that

. When
the bond is formed between two identical nuclei there can be no distinction between the
nuclei, and so the mixing coefficients (and therefore the orbital contributions), are equal.
The resulting molecular orbital becomes more accurately described as more of the
available atomic orbitals are included in the calculation. The variation principle states
that the lower the energy of the calculated orbital, the more accurately it describes the
actual molecular wavefunction.

Bonding and antibonding orbitals

The probability, p, of an electron in an orbital, ψ, being in an infinitesimal volume dτ at a
point r is obtained through the Born interpretation:

For H2

+

, the molecular orbital probability function is then given by:

P(r)=(ψ(A)+ψ(B))2

dτ=ψ(A)2

dτ+ψ(B)2

dτ+2ψ(A)ψ(B)dτ

This differs from the atomic orbitals as it represents the probability of finding an electron
in the two constituent atomic orbitals plus an additional term. This term has the effect of
increasing electron density in the internuclear region, and decreasing it in other regions
(Fig. 1a). Since electrons are waves, the enhanced electron density can be rightly
compared to the constructive interference of two waves. The enhanced electron density
between the nuclei enables the electrons to associate strongly with both nuclei
simultaneously, thereby reducing the free energy of the electrons, and so the molecule as
a whole.

The structure of a molecule depends upon the formation of bonds holding the nuclei in
their relative positions, and these result from occupied bonding orbitals (Fig. 1b).
Molecular bonding orbitals are derived from linear combination of atomic orbitals by the
addition of the component atomic orbitals, and act to decrease the free energy of the
molecule. The explicitly calculated result for H2

+

reveals that the next highest energy
solution to the Schrödinger equation is an antibonding orbital corresponding to the
subtraction of one wavefunction from the other:
ψ(MO)=ψ(A)−ψ(B)

Molecular orbital theory of diatomic molecules I 273

As with the bonding orbital, the probability function for this molecular orbital is given
by:

P(r)=(ψ(A)−ψ(B))2

dτ=ψ(A)2

dτ+ψ(B)2

dτ−2ψ(A)ψ(B)dτ

The negative term now corresponds to a decrease of electron density in the internuclear
volume of the molecule. The electron density decrease raises the energy of the molecule
above that of the free atoms. There is now a node—a line of zero electron density—in the
molecular orbital, between the two atoms (Fig. 1c).
It is usual to denote an antibonding orbital with an asterisk to distinguish it from the
bonding orbital. In the case, therefore, of two s orbitals interacting to form both a bonding
and an antibonding orbital, both molecular orbitals will be σ orbitals. The antibonding
orbital is denoted as σ*, allowing its immediate distinction from the bonding orbital, σ.

Potential energy curves

The degree of stabilization conferred on a molecule by the overlap of atomic orbitals is
heavily dependent upon the extent to which the orbitals are allowed to overlap. The
extent of the orbital overlap is in turn determined by the internuclear distance.
A potential energy curve may be plotted for a molecule, and is constructed by plotting
the energy of the molecule as a function of internuclear distance. For the bonding orbital
at relatively large separations, the energy decreases as the nuclei are brought together,
and the atomic orbital overlap increases. The total wavefunction for the molecule also
includes an internuclear repulsion term, which increases with increasing nuclear
proximity, and the energy of the

Physical chemistry 274

Fig. 1. (a) Electron density difference
between atomic 1s and molecular σ
bonds in hydrogen; (b) hydrogen σ
molecular bonding orbital; (c)
hydrogen σ* antibonding molecular
orbital.

Molecular orbital theory of diatomic molecules I 275

molecule increases rapidly at smaller internuclear distances. At an intermediate
internuclear distance, there is a balance between these two opposing effects, and the
molecule adopts its lowest free energy state (Fig. 2). For the antibonding orbital, the
decrease in electron density between the nuclei means that there is a fully repulsive
interaction between the nuclei at any distance, and this increases rapidly as the
internuclear separation decreases.

Fig. 2. Potential energy curve for a
bonding molecular orbital in a
diatomic molecule.

Physical chemistry 276

H4

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