Orbital

Molecular

MolerwlarOrbital|
Theory and Hydrogen Bonding
Theory (MOT)
Thstheorywas given by F Hund and RS Mulliken in
Consider there are two hydrogen atoms Aand Bin a
to explain the
lke in
order
theit
J012
relative bond strengths,charmagnetic
acteristicsnature
of
moletc.ecules hydrogen molecule, cach of which in its ground state
contains one electron in l-orbital.
Featuresof MOT The atomic orbitals of these atoms are represented by che
Salent
features ofchis theory are as follows
wave functions W and Wprespectively.
main
"Theelectronsina molecule occupy various molecular
The
Then, these aatomic orbitals combine bythe addition and
justlike the electrons of
subtraction of wave functions of individual atomic
orbitals
various,atomic orbitals. atoms are inpresent orbitals as shown below.
Molecularorbitals are obtained
comparable energies and
when atomic orbitals of VMO =VA tVB
proper symmetry combine Therefore, the rwo molecular orbitals G and o are
rogether.
. Whilean electron in an atomic orbital is under the tormed as o =V tp (Bonding Molecular Orbital)
infuenceof one nucleus, in a molecular orbital it is G=VA -V, (Anibonding Molecular Orbital)
underthe
influence of two or more
uponthe number
of atoms in the nuclei depending Bonding Molecular Orbitals
atomicorbitalis called
molecule. Thus, an The molecular orbitals obrained by the addition of
monocentric,
orbital,is termedl as polycentric.
while a molecular
atomic orbitals are called bonding molecular orbitals
number of molecular orbital (BMOs) and are represented by ¡ and t.
combiningobtained
.The is
cqualtothe
number of
atomic always
orbitals.
When two atomic orbitals combine, two types of
In the formation of these orbitals, the two electron waves
of the bonding atoms reinforce each other due to
molecular orbitals are obtained. One is constructive interference.
known as
bonding molecular orbital, while the other is known
8antibonding molecular orbital.
.The bonding molecular orbital because of their lower
energy have greater stability than the
antibonding molecular orbital. corresponding
.A molecular orbital shows the electron probability Constructive interference; amplitudes are added up.
distribution around a group of nuclei in a molecule.
.lust like atomic orbitals, the molecular orbitals are In these orbitals, che electron density is located between
Aled in accordance with the Aufbau principle obeying the nuclei of the bonded atoms because of which che
the Pauli's exclusion principle and the Hund's rule. repulsion berween the nuclei is very less.
.The bonding molecular orbitals are represented by Electrons present in a bonding molecular orbital tend to
G,t, 8etc., while antibonding molecular orbitals are hold the nuclei together and stabilise a molecule.
represented by o*, n*, Ñ* etc. Therefore, a bonding molecular orbital always possesses
lower energy than either of the atomic orbitals that have
furmation of Molecular Orbitals : Linear joined to form it.
Gombination of Atomic Orbitals (LCAO) Antibonding Molecular Orbitals
Acording to this method, che molecular orbitals are The molecular orbitals obtained by the subtraction of
bormed by the linear combination of atomic orbitals that atomic orbitals are called antibonding molecular orbitals
an akes place by addition and by subtraction of wave (AMOs) and are represented by o and .
hunctions of individual atomic orbitals.
 Al/none Chemistry o
164

In the formationof AMO,,the electron waves cancel (1) Similar symmetry f combining atomie
each other due to destructive interference. combining atomic orbitals must possess
symmetry about the molecular axis
he saty otbindy
same energy. If che orbitals have same
their symmetry is not same, they will not
aloenginergtyh bg
oof one atom can combine
C.g. 2p,-orbital25-orbital
comb
2p,-orbital or of the other
with che 2P, or 2p, -orbitals as their
atom but
Destructive interference; amplitudes ore substracted. different.
(iii) Maxímum overlap The combining
symmetie
In these orbitals, most of the electron density is located must overlap to the maximum extent.
atomic orbial
away from the space in berween the nuclei. extent of overlapping, more will be hee Higher
Infact, they have a nodal plane (on which the electron between the núcei of amolecular orbital. electron-
densicy is zero) in berween the nuclei and hence, the
repulsion berween che nuclei is high. Types of Molecular Orbitals
Incontrast to the bonding molecular orbitals, the electrons In case of diatomic molecules, molecular orbil. at
placed in these orbital destabilise the molecule because of (delta) etc. lf the
designated as a(sigma), n(pi), 6about
more mutual repulsion of the electrons in this orbitaltheas molecular orbital is symmetrical che
compared to the attraction berween the electrons and axis (or bond axis) it is called g-molecular otbital
is not symmetrical about the internuclear ax1s, it
internud,
nuclei which cause a net increase in energy.
Antibonding orbital
called molecular orbital.
(higher energy than that of atomic orbitals) Representing the orbitals in terms of signs of the
Molecular function, as s-orbitals are spherically symmetrical
Atomic orbitals Atomic orbital sign of their wave function is same in all the dir
orbital
VA- Va a>b Incase of p-orbitals, one lobe has ' signand the
has - sign. Overlapping of ' part of the electron2
of one atom with + part of the electron cloud of
VA VB second atom shows addition of atomic orbitals and
to the formaion of the bonding molecular orbial
Bonding ortbital The overlap of '+ part of the electron cloud of ope:
(lower energy than that of atomic orbitals)
with part of the electron cloud of the second a
Formation of bonding (al and antibonding shows the subtraction of the atomic orbitals and e
(o) molecular orbitals the formation of anti-bonding molecular orbital.
more than the A
few simple cases of the combination of atomic o
Note The energy of the antibonding orbitals is the energy are shown below
energy of combined atomic orbitals, whereas
of the bonding orbitals is lower than the parent orbitals. (i) Combination of s atomic orbitals The linear
However, the total energy of two molecular orbitals
orbitals. combination of l-orbitals centered on two nud
remain same as that of two original atomic gives two molecular orbitals that are symmetria
Conditions for the Combination of Atomic Orbitals around the bond-axis. Such molecular orbizals z

The linear combination of atomic orbitals to

form the o type and are designated as a ls and G.
Antbort
molecular orbitals is possible only when they satisfy the Molecular
molecla
following conditions orbitals
() Similar energy of combining atomic orbitals The Atomic d1s Atomic 1s 1s
combining atomic orbitals must possess the same or orbitay \orbital Bondrg

nearly the same energy. It means that ls-orbital can

, molecuä
1s
combine with another ls-orbital but not with
2s-orbital because the energy of 2-orbital is 1s 1s

appreciably higher than that of Ls-orbital. However,

it is not true in case of very different atoms.
 ema
/Bonding
and Molecular Structure 165

atomic orbitals
d2r
2s
Similary;.
orbicals
combine to give g 2s and
EXAMPLE 8. Label the molecular
orbitals formed by
orbitals
Combination
of 2p-atomic orbitals The the following combinations of atomic
namely three
2Px» 2p, and 2p, axes directed
(assume z-axis as internuclear axis).
alongthe X, yand|z coordinate are
porbioal
in (i) 2s + 2s (i) 2p, -2p.
regpectivelyIf z-axis is the (ii) 2p, +2p, (iv) 1s -1s
paxiswould internuclear axis, the xand
then be perpendicular to it. The (v) 2p, +2py
combinationof 2p-orbitals
results in MOs.types of
MOs,vie,sigma(o) MOs and pi()two
Sol. The MOs formed are
() 2s + 2s = G2s and o 2s
a)Formationofo-molecular orbitals It is the result of (ii) 2p,-2p, =12p, and r2p,
headonoverlapping of two 2p, orbitals, (ii) 2p, + 2p, = o2p, and olp.
internuclear axis. Thus, two along the (iv) 1s -1s = ols and ols
2p, atomic orbitals
combineto givetwo
molecular orbitals, i.e. (v) 2p, + 2p, =R2p, and r2py
MO(a2p.):and'antibonding MO(ß 2p;).bonding Orbitals
6)Formation of -molecular orbbitals These are Energy Level Diagram for Molecular
obrainedbysidewise overlap of2 p, and 2p, You have studied that ls atomic orbitals form two
which are not orbitals molecular orbitals designated as o ls and Gs.
symmetrical around the bond axis orbitals
becauseof the presence of positive lobes above and Similarly, 25 and 2p atomic orbitals (eight atomic
molecular
negativelobes below the
molecular plane. on two atoms) combine to give following eight
The molecularcorbitals obtained are designated r and orbitals.
.Ar-bonding. MO has larger electron Antibonding MOs G2s G2p, 2p. 2Py
l belowthe
densityabove Bonding MOs o2s o2 p. T2px 2Py
and
internuclear
axis. The -antibonding
MOIhas a node berween the nuclei. The energy levels of these orbitals have been determined
Molecular Antibonding ¡ experimentally from spectroscopic data for homonuclear
molecular orbital diatomic molecules of second row elements of the
Atomic
2lorbital
orbitals
Atomic
orbital
D-D-BD
2p,
2pz Bonding G
periodic table.
In the case of O, and F,, the increasing order of energies
molecular orbital of various molecular orbitals follow the order
2Pz
ol<o l<G2s<G2s<G2 p,<(r2p, sT2p,)
2pz 2p,
Molecular
Antibonding
molecular orbital
<(h2p, si2p,) <62p.
orbitals However, the above sequence of energy levels is not true in
Atomic Atomic 2py case of remaining molecules like Li,, Be,, B, Cz, N2.
lorbilta/ 12px \orbital t 2px
Bonding T For these molecules the increasing order of energies of
molecular orbital various molecular orbitals is

n20, 20, 2D, 8

n20,
Gl<o ls<G2s<62s<T2 p, T2 p,
Contours and energies of bonding and antibonding <o2p,<n2p, <n2p,
molecular orbitals formed through combinations of (a)
20, atomic orbitals and (b) 2p, atomic orbitals The important characteristic feature of this order is that
the energy of o2 p, molecular orbital is higher than that
Note r2p, or r2p, contains one nodal plane, whereas t 2p, or of n2 p, and n2 p, molecular orbitals.
i2p, contains two nodal planes.
 Allieone Chemistry

and
isseahle if N>N,<N,and
themolecule is unstableif Ny Ng=
the molecule
halfofthe
2 BondOrder
definedit is one
clectrons present
in the dibonding
f erence b
As already of
the numberorbitalk ie.
antibonding
(BO)=11/2(N, - N,)
Bond order
moleculeisstable.
moleculeisunstk
IfN,>N
=N,
IfN<N, or Ny
Bond
Notureofthe shows the presence of
3. or 3,it
order is L.2 respectively.
Ifbond triplebonds
doubleor
4.Bond-Length chehelpofbondorder.
measuredwith bond order
increa
Itis length decreases as the
Thebond
S5.MogneticNature molecule are doubk
orbitalsin a
the substanos
level
Molecular orbitals energy the molecular electrons,
diagram for O. F and Ne If all cwo
occupiedi.e. contains bymagnetic field).
diamagnetic(repelled molecular orbitals are sing
more
However, ifone or paramagnetic (attracted
molecule is
occupied, the e.g.O, molecule.
magnetic field).
Homonudear
Bonding inSome
DiatomicMolecules
there is on
Increasing
term homonuclear means that and di
Here the one element is
present
nucleus, i.e. two atom
type of
that the molecule is composed of
means given below.
molecules are
Example ofsome such
1. Hydrogen Molecule (H2)
hydrogen atoms combine te
(For Li,, Be, B,, C,, N,
molecules) It is formed when two one H-atom =l
Molecular orbital energy level
diagram for Number of electrons in
molecules
L,Bez, B.Cp and Ng
Behaviour Gls
Eledronic Configuration and Molecular
Energy

The distribution of electrons in

various molecular
of the
orbitals is called the electronic configuration following ls
i-Atomic
molecule. Electronic configurations gives the
Atomic orbital
orbital of H-atom
information which is given below. of H-atom ols
1. Stability of Molecules H H,
H

If the number of clectrons occupying bonding orbitals are Molecular orbital energy level diagra
represented by N, and the number of electrons for H, molecule
occupying the antibonding orbitals by N, then
 Bondingand Molecular Structure
| 167

electronsinH,molecule
of
Number
MOomliguration,
ofH, = l? em]+l=2.
N, =2 and N, =0 that he
From thet electonic configuration, We cansee
in
Thebondorder N, -N, are present in bonding orbital and 2e are present
antibonding orbital.
So, B.O =N, -N,4-2 =1
2 2 2
=lmearns that B,O =1 means thattLi, molecule is stable and contains
Rond
order the two hydrogen ho unpaired electrons. Hence, it is díagmagnetic.
togetherbyasingle
honded
atoms are
covalent bond. the bond
energy of
mol-! hydrogen molecule, has been found
dociation, 4. Carbon Molecule (C)
438 kJ and bond length equal to Ihe clectronic configuration of carbon is122p.So,
e
is no unpaired
74 pm. there are twelve electronsin Co.The electronic
there
Since, is electron the hydrogen
soi t diamagnetic. Its
in configuration of C, molecule is
molecule,
diagramis given above. molecular orbital energy
Molecule (Hez) From the electronic configuration we can see that b
formedwhentwo helium electrons are present in bonding orbital and 4e are
t ö of electrons in
Number
atoms =2.
one He atom combine together. present in antibonding orbital.
-N,
Energy o*ls
So, B.O, =
2 8-4-2
2
lt is diamagnetic in nature. It is important to note that in
C, both T-bonds are present, because of the presence of
1s tour electrons in two T-molecular orbtials. Generally, in
other molecules containing double bond, one is sigma
bond and other is T-bond.
¡ls
He He, He
S. Oxygen Molecule (O,)
Molecular orbital energy level diagram for He,
The electronic configuration of oxygen atom is
molecule 122p,So, there are 16 electrons. The clectronic
. Number of electrons in He, molecule =2 +2 = 4 e configuration of O, moclcule is
MO. configuration of He, =ol' o*12 O,:=ol'o* ' o2' o* 2: o2p; (2p: =2r2 p;)
Herc, N, =2 and N, =2 (r2p. =r*2p)
N, -Na _2-2 From the electronic configuration of O,, it is dear that
.The bondorder =
2 2 .=0 10clectrons are present in bonding molecular orbital and
6e are present in antibonding molecular orbital.
Rond order zero means that He, molecule is unstable and
des not exist. Similarly, it can be shown that Be,
molecule ols o*ls G2s o2 does not exist.
.:. Bond order
IN,-N,)=u0-6|=2
Bond order 2, indicates that atoms are held by a double
Uhum Molecule (i) bond. Further, two unpaired e are present in z2p.
tis formed when two lithium atoms combine together. and r* 2p, molecular orbital. So, O, is paramagnetic in
Number of electron in one Li atom is 3. So, there are six nature. Similarly, the electronic configuration of some
dectrons in Li,.The electronic configuration of Li, homonucear and heteronuclear molecules and their ions
molecule is can be found out, which is given in the table.
 Vdleterew ladey

95/2 P
14
9 ) 5/2

16
00-6)-5/2 Paey
17 17 00-7)=3/2 Pus
10-6)-1 Diar
10-8)-1 Diasge
17
10-7)= 3/2 Psrge
10-9)-1/2 Prp
00-10)-0 Doss n
He P0
10-9)=1/2 Prsrsg
19
10- 6)- 6/2 Paranp

14
oo-49-3 Diamage

Dlamag
14
 Bondng and Molecular Structure 169
eAl

Bonding Types of H-Bonds

which binds hydrogen
highly atom of one There are two types of H-bonds.
withthe electrisonegat
eoranother molecule calledivehydrogen
atom (,bonding.
Oor N) Itof
1. Intermoleculor Hydrogen Bond
dotted line. Itis molecules of the
Such bond exists between two different
bya
gd weaker than covalent H-bondin case of in
same or different compounds, e.g. etc. It resules
of HF molecule, the HF molecule, alcohol or water molecules
hydrogenatom of one hydrogen
molecule andbond exists
results in
association of two molecules and hence and solubility.
k nanother
n
molecule as shown
below. Aluorine increased melting point, boiling points
of
rom

hydrogenbond behaves like a bridge between two

Here
holds one atom by
A otS
hat
asher hydrogen bond. covalent bond and the H-bonds

fFormationof Hydrogen Bond -H-Þ

Thydrogens bondedto ahighly
Kthe electronegative element
sharedpairof electrons moves far away from Intermolecular hydrogen bonding in -nitrophenol
bydrogen
atom. Consequently, the
beomeshighlyelectropositive withhydrogen
respect toatom
the other 2. Intramolecular Hydrogen Bond
Since,there is displacement of Such bond exists when hydrogen atom is in between the
I ohehydrogenacquires partial positiveelectrons towards
charge (6*), two highly electronegative (F, O0, N) atoms present
within the same molecule.
shleNgains partial negative charge (8- ). It results in the e.g. In o-nitrophenol, the
) of apolar molecule with electrostatic force of
firmation hydrogen is in between
shown below.
atractionas the two Oxygen atoms. H-bond
Hô+
HoX...H° x..H°-xö This bonding prevents
the association of
Themagnitudeof H-bonding also depends on the Intramolecular hydrogen bonding in
molecules, making the molecule
ohysicalstateof the compound. In case of solid, it is molecule more chelarion 0-nitrophenol
Maximum
and for gases, it is minimum. in comparison of molecules where intermolecular
Thus,the bydrogen bonds have great influence onthe hydrogen bonding occurs. Hence, it decreases melting
structure and physical properties of the compounds. 3point, boiling point, and solubility. e.g, o-nitrophenol has
lower boiling point that p-nitrophenol.

Iopic Practice 4
1, Write the significance of a plus and a minus sign
5. Why is the energy of n 2 p, and 2p, molecular
shown in representing the orbitals. NCERT orbital are lower than o2 p, molecular orbital in
2. Write the important conditions required for the N, molecule?
linear combination of atomic orbitals to form 6. Is it correct to say that bond order always
molecular orbitals. NCERT increases when an electron is lost?
3. Can we have a diatomic molecule with its 7. Why KHF, exists but KHCl, does not?
ground state molecular orbitals full with 8. What is the magnetic nature of the anion of KO,?
electrons? Give a reason for your answer. 9. Out of H and H,, the latter has higher first
4 Use molecular orbital theory to ionisation
Be, molecule does not exist? explain why the
NCERT
energy while out ofO and O,, the former has higher
first ionisation energy. Explain why?
 Allnone Chemistry

specieshas
following the shm
the
Whichof NO, NO
13. bondlength? ,
ff Emehe relaive stabilje of the following NO,NO speciesin order of
following Lí;and
HEe Anl indicate their magnetie properties. Liz
0,0),0,of
Arrrangethestability,
14. increasing a
molecular
Liz,
orbíta| Justty
configra
compoundsin the
with
| Wha s the effect of followingprocess on the choice
the
following
order of
bondlength of
iond erder in N,and0,? Arrange
increasing [AsFl,KO,
O,
15. O,,
()N,Nj basis of
ground state
these eledrs
(00,0} +e Explainonthe dioxygenin
viscous than
molecue
N, to N; and configurationof H,0.
12, (0 How bond energy varies from isless
whyHF
why? what Explain
molecular orbital theory
(i) On the basisof between 16.
0s thesimilarity
(a) E, of (b) Co,N, NO"?

duplet).
chemicalbond. completeits
Summary constituentsof a
called
speciesis
completetheir
octet
(exceptH
whích

holdingvarious atomstryto symbol.

Force of
attraction
approach, calledLewis Hydrogenbond freeatom!
KoSsel-Lewis is
of anatom Covalentbond, electrons in the
electrons valance electrons)]
hocoraingto valance lonicbond, numberof
representthe bonds i.e. =[(total ie.
shaired
Notationof chemical structure bonding,
of Lewis number of
are threetypes an atomin the (total
Ihere
Formalcharge
on electrons)-1/2
pair
Formalcharge non-bondingi.e.lone 1
number of bondmultiplicity
-(total Bondlengthc
Bond parameters two nearestatoms. centralatom.
between nucleiof pairs aroundthe
Distance electron
Bondlength containingbonding gaseousphase.
orbitals mole of bondsin
the one stage, both af
Anglebetween to break compound.
Bondangle Amountofenergyrequired atoms in a cOvalent applied. Atbonding
and repulsion
two
Bondenthalpy formedbetween
Number ofbonds nuclei force ofattraction
Bondorder Between two
interactive
theory
Valancebond transferof only norone par
theseare balanced.
single structure. It involves
bonding by a
Theories of covalent properties cannotbeshown atom decides the
the
when all around the central
Resonance Required non-bonded) present
not ofatoms. electron pairs
(bonded or
ofelectrons, shell
Numberof valancy
VSEPR theory
molecule.
shape ofa
valance bond theory generated orbitals of same
Related conceptsto sigma and pi-bonds. and shapes to
overlapping createdby slightly different energies
Orbital intermixing ororbitals of
Hybridisation Phenomenon of sp,sp
important types are sp,
energy and shape. Its polar.
can be non-polar or bond. e.g. H, O, etc.
Polar character species similar atoms, non polar covalent expressed in termso
Covalent bond formed between two
called polar covalent bond, e.a. HCI, HE. It is
two dissimilar atoms,
Covalent bond formed between unit =Debye (D).
u=charge (Q) xdistance of separation (r)
dipole moment. Dipole-moment (u)