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Molecular Orbital Theory :

As per VBT formation a molecule involves are interaction between electrons of only those
atomic orbitals of the participating atoms which are partially filled. There atomic orbitals mix. with one
another to form a new orbital of greater stability while all other orbital on the atoms remains undisturbed
and retain their individual identity. But this cannot be correct because the nucleus of one approaching
atom is bound to affect the electrons waves of nearly all the orbitals of the other atom because In multi
electron system electrons are assumed to be waves. Besides this also VBT fails to explain the (formation
of coordinate bond) the paramagnetic character of O
2
molecules and the formation of odd electron
molecules or ions such as H
2
+
ion where no paining of electron occurs. So, to rectify all these facts a new
theory was put forward by Hund and Mulliken know as MOT.
According to this theory, all the atomic orbitals of the atoms participating is the molecule formation
gets disturbed when nuclei approach nearer. They all get mixed up to produce an equivalent number of
new orbitals that belong to the molecule now. These are called molecular orbitals. The electrons belonging
originally to the participating atoms are now considered to be moving along the molecular orbitals under
the influence of all the nuclei. Hence, molecular orbitals are polycentric.Molecular orbitals are of varying
energies and are arranged in the order of increasing energy levels as in the case of atomic orbitals
(defined only for homo nuclear diatomic specie).The filling of electrons is the molecular orbitals for
homonuclear diatomic species follow aufbau principle, the hunds rule and paulis exclusion principle.
Molecular Orbitals
(a) When the atoms to be bonded come close together, the orbitals of the bonded atoms lose their individual
character and fuse (overlap) to form larger orbitals called molecular orbitals.
(b) Like atomic orbitals, there are molecular orbitals in a molecule.
(c) The only difference is that in atomic orbitals, electrons move under the influence of only one nucleus (i.e.
AO are monocentric), while in molecular orbitals, electrons move under the influence of many nuclei
(i.e. MOs are polycentric).
(d) Molecular orbitals may, therefore be defined as the regions in space associated with all the nuclei of
the molecule where the probability of finding a particular electron is maximum.
(e) It may be noted that electrons in M.O. , are not confined to an individual atom, they belong to the entire
molecule and are said to be delocalized with respect to the individual atoms.
Important features of M.O.T.
(a) Like an A.O. which is around the nucleus of an atom there are M.O. which are around the nuclei of a
molecule.
(b) The molecular orbitals are entirely different from the atomic orbitals from which they are formed.
(c) The valence electrons of the constituent atoms are to be moving under the influence of nuclei of participating
atoms in the molecular orbital.
(d) The molecular orbitals possess different energy levels like atomic orbitals in an isolated atom.
CHEMISTRY Theory Notes on Chemical Bonding-MOT Quark
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(e) The shape of molecular orbitals are dependent upon the shapes of atomic orbitals from which they are
formed.
(f) Molecular orbitals are arranged in order of increasing energy just like atomic orbitals.
(g) The no. of molecular orbitals formed is equal to the number of atomic orbitals combining in .
(h) Like atomic orbitals, the filling of electrons in molecular orbitals is governed by the three principles such
as Aufbau principle, Hunds rule and Paulis exclusion principle.
Conditions for atomic orbitals to form M.O.
(a) The combining A.O. should be of a comparable energy.
(b) The combining atomic orbitals must overlap to a lager extant, greater the overlap, stable is the
molecule formed.
Comparison of Bonding and Anti-bonding M.O.:
Bonding M.O. Anti-bonding M.O.
1. Bonding MOs are obtained when two Anti-bonding MOs are obtained when two
AOs atomic orbitals combine together in such combine together in such a way that their lobes
a way that their lobes with + + sign or with + sign overlap.
sign overlap.
2. Wave functions of the two AOs are added Wave functions of the two AOs are subtracted.
3. The energy of BMO is less than that of both The energy of AMO is more that of both
the combining AOs the combining orbitals.
4. Formation of bonding MO leads to the Formation of an antibonding MO produces
formation of a stable bond between the repulsion between the combining atoms.
combining atoms.
5. The probability of finding the electron in the The probability of finding the electron in the
region between nuclei of the combining atoms region between the nuclei of the combining
is very high and hence a stable molecule is atoms is negligible. The electron density is
formed. concentrated only one nucleus at any
particular moment.
6. Each electron in a bonding MO contributes Each electron in an AMO contributes to
to attraction between the two combining atoms repulsion between the combining atoms.
7. The difference in energy between BMO and the The difference in energy between the AMO and
combining AOs is called stabilization energy combining AOs is called destabilization energy.
Comparison between sigma and pi molecular orbitals
Sigma molecular orbital pi molecular orbital
1. s-molecular orbital is obtained when + + or + p-molecular orbital is obtained when + + or +
portions of two atomic orbitals overlap each other portions of the two atomic orbitals overlap
along the internuclear axis. + + overlap gives with each other along a line perpendicular to
sbonding molecular while + overlap s-antibonding the intermolecular axis. + + overlap gives p
molecular orbital bonding molecular orbital while + overlap
gives p-antibonding molecular orbital
2. Sigma bonding as well as sigma antibonding molecular Since pmolecular orbitals are concentrated
orbitals have cylindrical symmetry around the inter perpendicular to the molecular axis, these
nuclear axis. It is for this reason that these molecular molecular orbitals do not have cylindrical
orbitals are called sigma molecular orbitals. symmetry around the molecular axis, i.e., these
molecular orbitals are antisymmetric about the
internuclear axis.
3.
b
x
s
and
*
x
s
molecular orbitals do not have the same
b
y
p and
b
z
p
molecular orbitals have the same
energy, i.e., these molecular orbitals are not degenerate. energy and hence are degenerate orbitals.
Similarly
*
y
p and
*
z
p
are also degenerate.
4. smolecular orbital can be rotated freely about the pmolecular orbital cannot be rotated freely
bond axis. about the bond axis.
5. smolecular orbital is a stronger molecular orbital, pmolecular orbital is a weaker molecular
since it results by the greater overlap of orbitals along orbital since it results by the lesser overlap
the nuclear axis. of orbitals along a line perpendicular to the
molecular axis.
6. The formation of a smolecular orbital decides the The formation of a pmolecular orbital does
direction and length of the bond (bond length) not decide the direction of the bond but shortens
the bond distance. The formation of the two p-
molecular orbitals shortens (as in a triple bond)
the bond distance to a greater extent than the
formation of one p-molecular orbital (as in a
double bond)
Comparison between atomic orbitals and molecular orbitals
Similarities
1. The molecular orbitals in a molecular or an ion have different energy and different shape and size as
atomic orbitals in an atom have.
2. The filling of atomic orbitals with electrons takes place in accordance with Aufbau principle, Paulis
exclusion principle and Hunds rule of maximum multiplicity. Molecular orbitals are also filled with electrons
according to these principles.
3. Like atomic orbitals, a molecular orbital can be represented by a wave function YY of an atomic orbital
is called atomic orbital wave function and that for a molecular orbital is called molecular orbital wave
function.
4. Each atomic orbital wave function in an atom is associated with a set of quantum numbers which determine
the energy and shape of the atomic orbital. Similarly each molecular orbital in a molecule is also associated
with a set of quantum numbers which determine the energy, shape and size of molecular orbital.
Dissimilarities
1. An atomic orbital is defined as the region A molecular orbital is defined as the region of
is in space round one nucleus in an atom in space round two or more nuclei in a molecule.
which there is maximum probability of finding
the electron.
2. An atomic orbital belongs to one nucleus only A molecular orbital belongs to two or more
and hence is monocentric. atoms (polycentric) i.e., a molecular orbital is
considered to be a charged cloud having all
the nuclei of the whole molecule.

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