Linear combination

of atomic orbitals

A linear combination of atomic orbitals

or LCAO is a quantum superposition of
atomic orbitals and a technique for
calculating molecular orbitals in
quantum chemistry.[1] In quantum
mechanics, electron configurations of
atoms are described as wavefunctions.
In mathematical sense, these wave
functions are the basis set of functions,
the basis functions, which describe the
electrons of a given atom. In chemical
reactions, orbital wavefunctions are
modified, i.e. the electron cloud shape is
changed, according to the type of atoms
participating in the chemical bond.

It was introduced in 1929 by Sir John

Lennard-Jones with the description of
bonding in the diatomic molecules of the
first main row of the periodic table, but
had been used earlier by Linus Pauling
for H2+.[2][3]

A mathematical description follows.

An initial assumption is that the number

of molecular orbitals is equal to the
number of atomic orbitals included in the
linear expansion. In a sense, n atomic
orbitals combine to form n molecular
orbitals, which can be numbered i = 1 to
n and which may not all be the same. The
expression (linear expansion) for the i th
molecular orbital would be:

or

where (phi) is a molecular orbital

represented as the sum of n atomic
orbitals (chi), each multiplied by a
corresponding coefficient , and r
(numbered 1 to n) represents which
atomic orbital is combined in the term.
The coefficients are the weights of the
contributions of the n atomic orbitals to
the molecular orbital. The Hartree–Fock
procedure is used to obtain the
coefficients of the expansion.

The orbitals are thus expressed as linear

combinations of basis functions, and the
basis functions are one-electron
functions which may or may not be
centered on the nuclei of the component
atoms of the molecule. In either case the
basis functions are usually also referred
to as atomic orbitals (even though only in
the former case this name seems to be
adequate). The atomic orbitals used are
typically those of hydrogen-like atoms
since these are known analytically i.e.
Slater-type orbitals but other choices are
possible like Gaussian functions from
standard basis sets.

By minimizing the total energy of the

system, an appropriate set of
coefficients of the linear combinations is
determined. This quantitative approach
is now known as the Hartree–Fock
method. However, since the development
of computational chemistry, the LCAO
method often refers not to an actual
optimization of the wave function but to
a qualitative discussion which is very
useful for predicting and rationalizing
results obtained via more modern
methods. In this case, the shape of the
molecular orbitals and their respective
energies are deduced approximately
from comparing the energies of the
atomic orbitals of the individual atoms
(or molecular fragments) and applying
some recipes known as level repulsion
and the like. The graphs that are plotted
to make this discussion clearer are called
correlation diagrams. The required
atomic orbital energies can come from
calculations or directly from experiment
via Koopmans' theorem.
This is done by using the symmetry of
the molecules and orbitals involved in
bonding, and thus is sometimes called
Symmetry Adapted Linear Combination
(SALC). The first step in this process is
assigning a point group to the molecule.
A common example is water, which is of
C2v symmetry. Then a reducible
representation of the bonding is
determined demonstrated below for
water:
Each operation in the point group is
performed upon the molecule. The
number of bonds that are unmoved is the
character of that operation. This
reducible representation is decomposed
into the sum of irreducible
representations. These irreducible
representations correspond to the
symmetry of the orbitals involved.

MO diagrams provide simple qualitative

LCAO treatment.

Quantitative theories are the Hückel

method, the extended Hückel method
and the Pariser–Parr–Pople method.

See also
Quantum chemistry computer
programs
Hartree–Fock method
Basis set (chemistry)
Tight binding
Holstein–Herring method

External links
LCAO @ chemistry.umeche.maine.edu
Link

References
1. Huheey, James. Inorganic
Chemistry:Principles of Structure and
Reactivity
2. Friedrich Hund and Chemistry, Werner
Kutzelnigg, on the occasion of Hund's
100th birthday, Angewandte Chemie, 35,
572–586, (1996), doi:
10.1002/anie.199605721
3. Robert S. Mulliken's Nobel Lecture,
Science, 157, no. 3784, 13 - 24, (1967)

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