(Molecalan Orbrtalheony

Chemical Bondang4
ounder stadlhe basic units of
matte hat make up he mateua world
The adtractive torce which binds he atoms togehe
wIhn a mole cule deined as chemical bond.
hee
Theue aue So many heories ee hat can ex plan
is chenical bond
Tupes ot chewical bands ane
Aonic or Clechovalert bond
2. Co-valent bond
3 Co-ovdinate bond
heories au Elechronic theory ot Valeny: kosse
Lewis
2. Valence Bond heory Pawling
slalba
3 Holeculax Bondheory Hund's
Muliken.
4. VSEPR heory (Valence shell
eleuron paiu
Dffeuence Between Valence bond Tpuliionheory
-
heor
heory and Moleca osbitalheory

Valence Bond heory Moleula Bondsheory

Atoms retain hei idivi-1 he Combining atomu JoOSe
oual identity even ate heiu individu ident1ty
bond fomation
22 Atonuc ovbitals ane mono-2
Atoie loleeulax orbitals ane
Poycenhic and elechons
centic elechon meves inhe
field ot one nucleus only. moves in he ield ot
two.cMnCTe \ Ueus
 Cont.
3 Valence bondhe.ory 3. HOT explain panamaqnetic
does not explaio 02 Paa ehavio ot 02
magnetic behaviou
4. t does not involvehe 4 At involvea he formation
formation ot bonding and of bonding and ani
orbita!. 0
antibonding bonding orital
Atoic ov bitals in ValeneS Moleculan orbitals ane
bondheory aHe leppres-
entel by SyPdf
Heprcsented by , K,
ec
6 The hätt flled AOs of G. The lled or unHlled
Valence shell Only take AOs oveuapp and take
Po in bond totmation Pau in bond tormation
Resonance
Plos
aca AHole
TResonance shasmoImpor
nit tant Yole inif.Dieety explain
tormation ot MO
Bond or deu can not be Bond ordeu can be deteu-
detcyined muned
Featwes ot Nolecala Orbtal heory
The atomdc orbitals overlap to tOTm new orbitals called
moleclan orbikals when two Aos Ovelapp o r
and torm n e
Conbine , hey ose heisidertity
0OT bitals Caled moleculax orbitals.
2 HOs anehe enegy
staBts ot a moleeule
ich he es the moleude axe tlled
Just a He eneuy States
atomic avbltala aNehe
of an atom in whichhe es ot hel atonm axe
Hlled
3 A Mos gveshe probability distnbukHon
l o un d a TOup of
at m u c l e J u t as AOs
AOs
 he é pro bability distibuion aound he single
Aule nueleus
Onyhose atonic Orbitals can combine to tom
4. Oy enegles and prope
compaable
HOswhich have IS can Combine wih IS not 2S
Orientation for e
Cambining
of Hos formed. is
equalto
5. The
Ihe numbe
orbitalsb.
atomic oritals
form two new

two A0s Combine hey

6 when
Called BHOs a ABNOS and
and hence
hene

Bonding Mos
MOS has uowe ene
The AMOS
reateA stabtlity henhe CoTresnding
8 whexe
he MOs
The
are Heprsentattd by oT,

ABHOS ane UHeprcsenting by r*S*

as upon h e

MOs tormel depend pon

The shape of A0s
A0s
of
o f he Conbinin aceordinq to
tpe according
HOs takes place
takes

lo The
The llin o
lling Hund's rule
Prdciple, Panli Exclusion
Aufbau
otmaximum multiplicity

Combination
S *IS
IS +1S
S *2S
2S+AS

2sp * 2SP
P +2 S
2 Px+ Px
Py *2Py
+2Py
Pz+Pz

Pictorial Reprscntion
Bondina
+
S
 b

SP
S
+
P
SP
+
+

X-

*Py
Linea Conbinad ton ct Atomic Oxbitals LCAO)
meehancshe Ao be Cam exprmsse
Acc. to wave
tunmctlon (w) which epruent h e anpli-
wave
waves hese value ean be
tude of eleetron Schrodinge wave
h e soluhion
from
Calculatcd
c a n be applie +o meledle by aing
eguation which
LCAO meho d
two atoms A B havin
atomic orbittals ot
Two
wo
Chage density
ot atom A B
CPA) pB)
hein wave tunction Two
Q
r peetively
Possi biliie aHe
 I MOs ae addition of Cv)
tormed by he
wawe ot atomic orbitals known as BNO haung
tunction of

ulow enenay impaus high stability when e

cloud & proach eaeh öthea CSupeuimposed wh
ot two oybital have Cume Sign
region phase toumed
OY both a e in Sqme
Same sign indctexence
additHve Combinckion C Conu uetive
PA+VB subhrachon
orbital je tormed by the
ti) Tf mole cula
Ot wave tunction ot AOs known as ABMO having
2 impats dowen stabiltty
whene
high eneg1
(Superinpo'sed rgion
clou approah eaeh ohen ) wh
have dHteuert sim
two ariitals phase in ditfeuent
dittenent sgn or boh ate

teumed a Subtracive combinakion C Desutive

intcuteence )
PAPB
ab othe wave
2
ndicatts e change densities
PA 4(Va2indicates probabilit
Probability
function while tom (vb)2
ABMO Hespectively
ofe in BHos *s and
densty
olensity

>'A+V tom 2AYe (v»)*

han
ot e in BHOs is qreatu
Ths probability denaity is
ot e in ABNo S
of probability odenaity
he Sum
ot e in AoAO by
o wex
honhe prolabilî ty denity
2PAPe
(a) h
 L2

Heavie Holecue

e O ,0,0 O
2
e>14 Chigheu) C Heavie moteoats

Moleeles) y 4"
e4 CightoH ' x

ISIS2S2S72Py=n22
Ta*2R r*2Pz
Ligktea Molecules
E e q H e ,Me i , Ba, Be.
CO,CN C N2 N2 N2
Rules ot Oveulap should
toTmation ot NOs
i
involved.
he
axe
AOS approxi matey ot Same eneg
extents
exttts
be to a Consideable
Considenable
In
oveulp
2 Aos must
bonds incaeases e chage density
chage
Stable
to torm
between two nuelei wh
Symmey
AOs must havehe he Same
3 AOs
rCApect to
mele cuwdan axis.

Note between 2S 2 AOS

2p A0s
ffenence
akom
The
Smal
ene0( e<H)
Ceg14) orbital of one
2S

ot Second atom.
of
Close to 2Px aybital
Same Symmety
wo orbitals aHe
As he
Can-not be 19nored As a Hesutt
hei Oveulap atom
nteaetion between S orbital of one
S&2s
wh POrbital at adhey A
vice veHsa
6
 S- chaHactey 4 2P
not rctain heiu pwte
do n o t Hetalnheiu P e P- chanac
2Px
te is qiven by he
h one
e one
Ihe bond ordeu
Bond ovdex between no einin bonding
halfhe ffeue nce

and antibon dingq MO

MO
Bond Orde"= 2 N-Na)
N e s in BNO
Na es in ABNO
- no bond formation (zero)
Na- N
Na>N - Unstable

in prcdicting stability of
Bond orde helps
molecule
Stable B-OI -

siqle bond
NgNa d
8O 2olouble bond
BO 3 triple bond

A all es ane paiued in

Magnetic Behaviou
Ho Conhignaion - Diamagnehie

4t O es aue unpalne in Ho coniqunation

anomaq nehc
Stability
B O Stability Bond disso
Ciaion
ene
BO
Bond lengh
 hanacteustcs ofbon ding MO
Posses dowe encHo h a n combining, AOs

posses igh edaity

3 T Ipauts stability to he meleule.
Evey e in it makis Conbi bution to the attrachion
tuoo Conbining atoms
at
Iis ony omed whenthe dobes or Sides
he
h e Conbining aBomic orbitals possehe same
sigh.
6 Bonding HOs a e obtaincd by addition ot wave

functioN of
ot atomsCadditive conbinahion)
Chaacteistica of Antibonding Mo
MO

posse highe enegyhan Conbining A0s.

AOs
2 possesdouo e &enaity
stability to h e molele
3 It do not inpans
in iE makes conibution tohe nepl-
Eveuy
sion of
tuo Conbining atons
tormed uheh he dobes Or Sides
5 IH is ony
atomic arbltals Posseshe
of h e cbnbining
HfeuenF sign otwave
subtraction
6 ABMO aHe obtained by
function of atom 0
o subtrachive conbination

C2 N 02 FF2 Nez
HHeLi be B 16 18 2-0
8 lo 2 4
24 6 o B O
O 2 3
 MoD
N2 N+N CHoMO DIATOMIC)
1+1 - 14
MOC
2 2 2

E
B0 (lo-4) -3

RRPy 2P2

P 1 P
E

1K
2S

k.k
CIs-IS) N
N
Bi ,C2 siilan
H, He, Li1y Be
wa

O2, F, Ne Heavie Moletles

 2
2

E
BO Clo-6) -2
Magnehic Behaviou Paramagnetic

1uh1
2P TaP2 2P

Px
E

1
1

1
S

kk
CIS-1S)

lo
No CHeteno diatomic mole cules)
Nt0 = NO

7+8 I5
2 2 2 2 2

E
P

P 7 ralz 11
2P
E

S
1K
2S
2S

S
1sHS
N

HF/HCI HF H-S
F-IssaP5
CIS-2 *(IS-?Pz

IS-Rz BO-R-)
1
IS E
11 P5
1

Is2

11
The atomic orbital enegy uevel s ane H is (-12-6 lev)
F S C-Ho 1ev) A P (-18.6S e) So eneg dUfeAence
diterence
must be
F Can
13 evhe ovbitals
Ovelap
of is ofh4 aP of
to form T bond due
enegy Due
compah ble
to high e negativity oitfeuente 4 high
atomc no diffeence IS ofbital ot H
ean-no
Ovelap wih IS 2 s of F. The es ot S A2s
of P Temain delocallised in atomic orbital ot
F atomhus shuetwe is distortd.
Co I+ lonized to give Cot by emava ot one
e Co Clo-4) - 3
2

3-Co -

bond lengh 128 AO

5-Cot
B.0 Doeanot matche
Bleng
is
So assumed Iproposed Co ConHguaton
2 2
IS *IS S

E
So eemoved thom antibonding Ho s )
CO 3 128 AD

matches
Cot 3.5 15 A
2P
2P

aS
L
CO

13