The molecular orbital or the orbital wave function represents the frame of the molecule that describes the

distribution of spatial probability density for a particular electron bound to the group of nuclei.
In the molecular orbital treatment, the electrons of the bonding shell of the central ion, as well as those of
the ligand atoms, cannot be exclusively attached either with the central ion or with the ligand nuclei. The
electrons are mutually linked, to some degree, with each of them.
When molecular orbital theory is understood, we can easily explain:
 the electronic structure of molecules;
 the symmetry of molecular orbitals;
 the relative energies of the molecular orbitals; and
 how the electron distribution changes upon going to some low-lying excited electronic state.

THE LINEAR COMBINATION OF ATOMIC ORBITALS-MOLECULAR ORBITAL (LCAO-MO)

AND HUCKEL APPROXIMATIONS

Definição orbital molecular: The orbital, atomic or molecular, is a one-electron function; it is an

eigenfunction of a one-electron operator. For atoms, we defined the atomic orbital in terms of the eigenfunctions
of the one-electron atom, i.e., the hydrogen-like atom. The physical significance of the atomic orbital is that it
gives the probability of finding the electron that is assigned to it. Though the orbital was defined for the one-
electron atom, we saw that it was possible to extend the use of this concept by constructing manyelectron
functions from the one-electron functions.
These same ideas can be applied to molecules. Here we can start by defining molecular orbitals for a
one-electron molecule. We can then extend the use by constructing molecular orbitals for many-electron
molecules.

(Principles of Quantum Chemistry Por David V. George)

A aproximação de born-oppenheimer assume que o núcleo possui posição fixa no estudo das funções de
onda do elétron, essa aproximação se justifica pelo fato pelo núcleo se mover muito lentamente em relação aos
elétrons em razão da sua massa ser centenas de vezes maior que a massa do elétron.

LINEAR COMBINATION OF ATOMIC ORBITALS

which single electron wavefunctions (molecular orbitals) are represented as linear combinations of
atomic orbitals
The most generally used method is that called the linear combination of atomic orbitals (LCAO) method; this we
shall now describe. We further recall that to do this in a systematic way it is necessary to choose a trial function
with one or more parameters that can be varied to give the function corresponding to the lowest energy. In
molecular problems we can obtain a trial function by taking a linear combination of the atomic orbitals of the
atoms that form the molecule. If an electron in a molecule is near one of the nuclei, we can expect that the effect
of this nucleus on it will be much larger than the effect of any of the other nuclei; consequently, it is reasonable
for us to assume that the molecular orbital in which this electron finds itself is similar to the atomic orbital
associated with the nucleus in question if it were not part of a molecule. In the LCAO method we assume that
this approximation can be used as a starting point even when the electrons are not very near particular nuclei.
The variation theorem then allows us to determine the best molecular orbitals that we can construct from a linear
combination of the atomic orbitals.

H is the correct Hamiltonian; E0 is the lowest eigenvalue of this Hamiltonian.

We now have to minimize the left side of Eq. (10-12) by finding the best values for the a's.
We saw in Section 10-6 that the very simple MO treatment of the hydrogen molecule did not give very good
results. In the last section we have seen that the simple treatment can be extended to more complex molecules.
Considering the extent of the inadequacy of the simple treatment for the hydrogen molecule, we might expect
that for both this molecule and for more complex molecules considerably more sophistication would be needed
to obtain satisfactory results. In fact, there are several improvements that can be effected in the MO method.

it is important to remember that these orbitals are mathematical constructs which only
approximate reality. Hartree-Fock theory was developed to solve the electronic SchrÄodinger
equation that results from the time-independent SchrÄodinger equation after invoking the
Born-Oppenheimer approximation.

pretending that the electrons don't interact with each Other If that was
true, then the Hamiltonian would be separable, and the total electronic wavefunction ª(r1; r2)
describing the motions of the two electrons would just be the product of two hydrogen atom
wavefunctions (orbitals),
pretending that the electrons ignore each other is a pretty serious approximation!
the Hartree-Fock method seeks to approximately solve the electronic SchrÄodinger equation,
and it assumes that the wavefunction can be approximated by a single Slater determinant
made up of one spin orbital per electron.

variational theorem, which states that the energy is always an upper bound to the true energy.

For symmetric energy expressions, we can employ the variational theorem, which states that
the energy is always an upper bound to the true energy. Hence, we can obtain better
approximate wavefunctions ª by varying their parameters until we minimize the energy within
the given functional space. Hence, the correct molecular orbitals are those which minimize the
electronic energy Eel! The molecular orbitals can be obtained numerically using integration

Hartree – Fock – Roothaan (HFR)

Hartree-Fock theory is fundamental to much of electronic structure theory. It is the basis of
molecular orbital (MO) theory, which posits that each electron's motion can be described by a
single-particle function (orbital) which does not depend explicitly on the instantaneous
motions of the other electrons.
density functional theory (DFT)
Hückel Molecular Orbital Theory
An approximation introduced by Hückel in 1931 considers only the delocalized p-electrons moving in a
framework of σ-bonds. In many exercises where only π systems are considered, we will employ Hückel
calculations.

Fenske – Hall molecular orbital theory

method that contains no empirical parameters, which began almost 40 years ago in the research group of Richard
F. Fenske. We demonstrate for transition metal complexes that the non-empirical Fenske – Hall (FH) approach
provides qualitative results that are quite similar to the more rigorous treatment given by density functional
theory (DFT) and are quite different from Hartree – Fock – Roothaan (HFR) calculations which have no electron
correlation.

The method is an approximate self-consistent-field (SCF) ab initio method, as it contains no empirical

parameters. All of the SCF matrix elements depend entirely on the geometry and basis set, which must be
orthonormal atomic orbitals. density functional theory (DFT). (The self-consistent field method is an  iterative
method that involves selecting an approximate Hamiltonian, solving the Schrödinger equation to obtain a
more accurate set of orbitals, and then solving the Schrödinger equation again with theses until the results
converge.)

Originally, the impetus for its development was to mimic Hartree – Fock – Roothaan [5] (HFR) calculations
especially for large transition metal complexes where full HFR calculations were still impossible