The overlapping atomic orbitals can differ.

The two types

of overlapping orbitals are sigma and pi. Siama bonds
occur when the orbitals of two shared electrons overlap
head-to-head. Pi bonds occur when two orbitals overlap
when they are parallel. For example, a bond between
two s-orbital electrons is a sigma bond, because two
spheres are always coaxial. In terms of bond order
single bonds have one sigma bond, double bonds
consist of one sigma bond and one pi bond, and triple
bonds contain one sigma bond and two pi bonds
However, the atomic orbitals for bonding may be hybrids
Often, the bonding atomic orbitals have a character of
several possible types of orbitals. The methods to get an
atomic orbital with the proper character for the bonding is
called hybridization
 VB theory today
Valence bond theory now complements molecular orbital
(MO) theory, which does not adhere to the VB idea that
electron pairs are localized between two specific atoms
in a molecule but that they are distributed in sets of
molecular orbitals which can extend over the entire
molecule. MO theory can predict magnetic properties in
a straightforward manner, while valence bond theory
gives similar results but is more complicated. Valence
bond theory views aromatic properties of molecules as
due to resonance between Kekule, Dewar and possibly
ionic structures, while molecular orbital theory views it as
delocalization of the T-electrons.
The underlying mathematics are also more
complicated limiting VB treatment to relatively small
molecules. On the other hand, VB theory provides a
much more accurate picture of the reorganization of
electronic charge that takes place when bonds are
broken and formed during the course of achemical
theory
reaction. In particular, valence bond correctly
dissociation of homonuclear diatomic
the
predicts
molecules into separate atoms, while simple
molecular orbital theory predicts dissociation into a

mixture of atoms and ions.

More recently, several groups have
developed what is often called modern
valence bond theory. This replaces the
overlapping atomic orbitals by overlapping
valence bond orbitals that are expanded
over a large number of basis functions,
either centered each on one atom to give
a classical valence bond picture, or
centered on all atoms in the molecule.
 Applications of VB theory
An important aspect of the VB theory is the condition of maximum
imum
Overlap which leads to the formation of the strono
bonds. Tthis theory is used to explain the covalent bond formation in
many molecules.
FOr Example in the case of the F molecule the F- F bond is
Tofmed by the overlap of pz orbitais of the wo F atoms, each
overlappina orbitals are ciferenti o e the bond
strength and bond lengths differ between H, and Fz molecules.
I n an HF molecule the covalent bond is formed by the overtap of the
1s
orbital ofHand the 2pz orbital of F, each containing an unpaired
electron. Mutual sharing of electrons between H and F results in a
Covalent bond in HF.
Molecular
In
orbital theory (MOT)
chemistry, molecular orbital (MO) theory is
a method for determining molecular structure in
are not assigned to individual
which electrons
bonds between atoms, but are treated as
moving under the influence of the nuclei in the
whole molecule. Molecular orbital theory was
seen as a competitor to valence bond theory in
the 1930s, before it was realized that the two
methods are closely related and that when
extended they become equivalent.
Overview
Molecular orbital (MO) theory uses a linear combination
of atomic orbitals (LCAO) to represent molecular orbitals
involving the whole molecule. These are often divided
into bonding orbitals, anti-bonding orbitals, and non
bonding orbitals. A molecular orbital is mereiy a
Schrödinger orbital which includes several, but often only
two nuclei. If this orbital is of type in which the electron(s)
in of
the orbital have higher probability being between
a
nuclei than elsewhere, the orbital will be a bonding
orbital, and will tend to hold the nuclei together.
I f the electrons tend to be presentin a molecular
orbital in which they spend more time elsewhere
than between the nuclei, the orbital will function
as
an anti-bonding orbital and will actually
weaken the bond. Electrons in non-bonding
orbitals tend to be in deep orbitals (nearly
with
atomic
orbitals) associated almost entirely one
nucleus or the other, and thus they spend equal
time between nuclei or not. These electrons
nor detract from bond
neither contribute
strength.
Spectroscopy and Energy Levels
At the next level of detail. I would point to the
spectroscopic data, which has been around for
over 100 years, as strikingly direct evidence for
molecular orbitals.
and the
A good way to visualize the orbitals, filling
of orbitals, is to draw energy level diagrams such
as figure 20 through figure 23. In all such
diagrams, energy increases vertically. The energy
is not shown to scale, but the ordering of the
levels is shown correctly. The electrons in the
core levels are
shown in ingray, because they
almost never participate chemiqal reactions
The bonding versus antibonding character of
each level is encode three ways in the
diagram: The tips of the level turn up for
bonding levels, and turn down for antibonding
orbitals. The name of the level has a "*" in it

for antibonding orbitals, and not for bonding

orbitals. Finally, off to the right, the levels aree
explicitly labeled "antibonding" or "bonding"

The name
the
of eachIeveltells us something
orbital
about symmetry of the molecular
wavefunction, and about how it can be
derived from the atomic orbitals
that make up the molecule.
of the atoms
I n all of these four cases, there are three high-lying
antibonding orbitals. Figure F2 Energy Levels

g2Px antibonding
2P2 T*2Py antibonding
2Pz 2Py bonding
62Px bonding
s' 2s
antibonding
2s bonding
1S antibonding9
cos
Levi d1s bonding
 o, Energy Level

g2Px antibonding
2Pz 2Py antibonding

2P2 2Py
2Px
bonding
bonding
G 2s antibonding
2s bonding

g1s antibonding
Core
Levels 1s bonding
 1)=5 valens
ence clecum
C++
l+

9 Ntregen, N, couibute.

ular othitals
2p;.2P,2p) wouid have eg
Eachof the two N-aloms (1, 2/, molecule
contigration cule is

and four ate modoculie

the electronic
sowands e
ele tas
and ten
ta antobonding orbital
represented as given in Fie. 6.38 molecular
orbitals
and ony
There are eight electrons in the bunding Na o s
are bondeu
witn three covalent
nd
e two
g y e s the mumber of bends 8-21A electron
unpaired
it has
no
as
diamagnetic
Atple bond. N, molecule is
a total of 2 ( 2 + 2 + l - 1
Een, O, 2P;) contnbute
2p, 2p,
oxygen atoms (ls, 2 ei
1here are

paling orbitals
towards the Osygeh meoecule.
atomic 6.39.
12 valence electroas and 2 x 4 8
ulat orbitals ànd 12 electrons are accoma
c

2p

ATOMIC ORHITALS
OFOAOM ATOMIC ORBITALS
OF O ATOM

MOLECULAR ORBITALS
OFO, MLECULE

Fig 6.39. Molecular

ortals of O,
antihondingg orbutals; andmolecule,
alli the
having one full, two half-filled and one v

bonding molecular orbitals are full

 MO theory provides a global, delocalized perspective on
chemical bonding. For example, in the MO theory for
hypervalent molecules it is unnecessary to invoke a major
role for d-orbitals, whereas valence bond theory normally
useshybridization with d-orbitals to explain hypervalency.
In MO theory, any electron in a molecule may be found
anywhere in the molecule, since quantum conditions allow
electrons to travel under the influence of an arbitrarily
large number of nuclei, so long as permitted by certain
quantum rules. Although in MO theory some molecular
orbitals may hold electrons which are more localized
between specific pairs of molecular atoms, other orbitals
may hold electrons which are spread more uniformly oveer
the molecule. Thus, overall, bonding (and electrons) are
far moreindelocalized (spread out) in MO theory, than is
implied valence bond (VB) theory. This makes MO
theory more useful for the description of extended
systems.

m, is presenting
 b
Thebenaing vus stoondig chcr of
or The Bes at te isvai hur

artath tse nene of the inee

DOu he y e t r y ef e mocular ortrt

tred frem the aerie artdte at iheatoms

Figure: N Energy

17
g2Px antibonding
2Pz 2Py antibonding
6 2Px bonding
18
2P Levels
2Py bonding
o2s antibonding
2s bonding

9
Core G1s antibonding
Levels o1s bonding
 Feater about
ut the
the line joinin the
two nucle
The regio
B O N DO R D E R of overlapislesser
How ma anv are the bonds in a
molecule Bond order
heory
Orbitaltheory The number of bonds
in
or
is
correctly predicted by the Moleuular
of
plectrons i n in the bonding molccular a molecule is one-half of the difference of the
o Mathematically, orbitals and the number of number of
o v b i t a l s

electrons in the antibonding molecular

No. of electrons in
No of elecrons in
Bond crder bonding orbitals
antibonding orbitals
Na
on practice, only MOs formed from valence
In commonpractice
orbitsls are considered for
order determining bond
e oredicted bond orders are found to be in
nsMolecular Orbital theory helps in conformity with other methods of determining it
establishing whether the existence of abond is feasible
wmot, For instance, the formation of He, molecule, discussed in the following section, completely
led out as the bond order predicted is zero. is

In general,
(0Amolecule is stable if N, >N,
()A molecule is unstable if N, <N,
Information given by Bond order
Nazrul lslam, is presenting .
 und to b
tound be in cont
Molecular Orbital theory helps intoestablishingmity with other methods of determining it
whether the existence of a bond is feasible
esot. For instance, the formation of He, molecule, discussed in the
ed out as the bond order predicted zero.
is
following
section, ls
compleiely
In general,
0A molecule is stable if N, > N,
Amolecule is unstable if N, <N,
nformation given by Bond order
The bond order as determined by the above formula is very helpful as it gives us the folowing
aluable information
(0 Stability of the Moleculefion
Amolecule/ion is stable if N, > N,
() Bond Dissociation Energy
hdepends upon the bond order. Greater the bond order greater is the bond dissociation cnergy
(ait) Bond Length
Bond order is inversely
proportional to the bond length. Higher the bond order, smaller the bon
ength
() Magnetic Properties
epresence of unpaired electrons in Moleylar orbitals of a species makes it paramagneti
reGreater the number of unpaired electrons, the more will be its paramagnetic character
he other hand if there are no unpaired electrons in MOs the species will be diamagnetic in natur
hand,
l Islam, is presenting
 s O N DO R D E R
Tempnf evel w leser

g0 y are the beinds in a

molecule or Bond erder
Y The number ef bonds in c l y prediced by the Molecalar
is

ob a moleule
he bonding molecular ortitls and the eisr
one lalf of the dilece f the
italk Mathematically, of elecosis e number of
aibonding melecular
No ef e m s

Bder ( bonding ) (
og
iei
)

In enon practice, only MO formed from valence

orls are coidered foe
detemining bond
epredicted bond onders are found to be in
conformity with other mctiods of detemining
nas Molecular Orbital heory helps in establishing whether the existence of a bond feasible is

met. For instance, the fomation of He, molecule, discussed in the following sectiom ls
compleels
as the bond onder
sedout predicted is zero
I general
DAmolecule is stable if N, >N,
Amolecule is unstable ifN, <N,
Islormation given by Bond order
The hond order as determined by the above formula is wvery helpful as it gives us the followins
aluahie information
n Stability of the Moleculeion
Amoleculefion is stable if N,>N,
() Bond Disseociation EnerEy
h depends upon the bond order. Greater the bond order greater is the bond dissociation cnerg
(n) Bond Length
Bondorder is inversely proportional to the bond length. Higher the bond order, smaller the hor
ength
(i) Magnetic Properties
Thepresence of unpaired electrons in Molecular orbitals of a species makes it paramaynetic
character
Gireater the number of unpaired electrons, the more will be its paramagnetic n
the other if there are no unpaired electrons in MOs the species will be diamagnctic
natum
hand,

nting
 enoi their molecular
Let us nopw construct he molecular energy
( )NITRICOAIDE (NO) iagram for some
heteronuclear molecules.
The nfiguration of participating N and O
electronic confi

N= 1s 2s 2p. 2p,' 2p, (5 valence

atoms are
electrons)
Is 2s
O= 2p. 2p, 2p, (6 valence electrons)
number of valence electrons is 11 and
The total
electronic configuration of NO
written a s
molecule can b-
NO KK o(2s) (2) a(2p,)r (2p,) r
(2p,) n* (2p,)
The bond order
-N,-N,
(8-3)
-2

TC(2py)) TC ()
 are how able
HOMONUCLEAR roMIC MOLECULES
tohH
o f Molecular
Orbital theowe ouamic
e
homonucicalr molecule
Alter huving dhcussed the basic prna f
o
some of the cules
and bonding propertie
p the electronic structures of t a o s
They give rise
to twe
() Hydrogen, H, orbitals

irom Ls' atoemic teo De accommodated in e

molecule is formed
ciecirons
two
e has
The molecule Both these
filling. lectros
ele

bitals
oç la) and a'is) Aufbau
by
order of

molecular orbitals and arefilled as desired antibonding

orbital remains ant. The
wO and the
molecular orbital
the lov n e r y binding
elect
ctronc configuration of the molecule is represcnica
2H(lr) Halsa(la

- ATOMIC ORBITAL
OF H ATOM
ATOMICORBITAL
OFHATOM

l
MOLECULAR ORBITAL
OF H, MOLECULE

636. Mode of Molecular orbital filing in Hydrogen molccule

Fig

The number of bonds in the molecule, accordingly is(2-0)=1. Thus two hydrogen atoms

are bonded through only one bond in the molecule.

(2) Helium, He
Helium atoms have the configuration Ls'. For the formation of He, the molecular orbitals required
are a (ls) and a"(ls) which have to accommodate four electrons (two cach contributed by the atoms
Each one of these molecular orbitals would
accommodate two electrons as shown
below.

ATOMIC ORBITAL
OF He ATOM ATOMIC ORBITAL
OF He ATOM

u)
MOLECULAR ORBITAL
OF He, MOLECULE
Fig 6.37. Molecular orbhital
diagram for He, molecule