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Chapter 14
Covalent bond:
2 4+1=5
3
3+2=5
5
2+3=5
Solution for Molecules
Based on Born-Oppenheimer Approximation:
nuclei being much heavier than an electron, move
relatively slowly and may be treated as stationary while
the electrons move around them.
Enable to solve
Schordinger
equation for the
electron alone
at a fixed
location of Re: Equilibrium Bond Length
nuclei. De: Depth of the minimum
VB Electron
Density of H2
A B
Bonding in N2
Nitrogen 2pz
orbitals pair
Cylindrical
Symmetry: bond
Nitrogen 2px and
2py orbitals
No cylindrical
symmetry: bond Sigma and Pi bond formation N2
VB Theory of polyatomic molecules
2 1 1 1
e.g. H2O molecule: O atom : 2 p x 2 p y 2 p z H atom : 1s
2p orbitals of
oxygen form
bonds with H1s
Predicted bond
angle: 90o
Deficiencies of VB
Poorly estimates bond angle
Number of bond formation, e.g. C(2s2p2)
Promotion of electron: Hybridization
e.g. Methane CH4
Promotion of one electron from 2s to 2p orbital of C
atom: 2s1 2 px1 2 py1 2 pz1
(sp3 hybrid
h1 s p x p y p z
Atomic orbitals inter-mix to
orbitals)
h2 s p x p y p z
give rise four new orbitals
h3 s p x p y p z
called Hybrid orbitals
h4 s p x p y p z
Sp Hybridization: Linear
Two bonds with hybrid orbital of another C or H1s.
Two bonds perpendicular to molecular axis
Hybridization: summary
c A A cB B
Antibonding
MO Theory of diatomics
Antibonding Orbital
Bonding Orbital
Higher energy than the
Constructive interference
bonding orbital
Electron accumulated in
Nodal plane, destructive
the internuclear region
interference on this plane
Electron relocate outside the
bonding region
Bond Formation
Lower energy in bonding orbital ()
Higher energy antibonding orbital (*)
For, H2+ ,
bond length: 130pm (106)
For H2
bond dissociation energy :171 kJ mol-1 (250)
Orbital Symmetry
Inversion Symmetry Same Sign, Gerade Symmetry)
Behavior of when it
is inverted through
center of inversion.
identical sign of
around center of
molecule (Gerade Opposite Sign, Ungerade Symmetry)
Symmetry)
Opposite sign of ,
(Ungerade)
Symmetry
Symmetry and Overlap
e.g. S and p overlap
AO MOs AO
Electronic Configuration of N2
No. of Valence Electrons: 10
Ground-State
1g2 1u*21u42g2
Bond Order
b= ()(n-n*) (For N2 , b=3)
n=number of electrons in
bonding orbitals
n*=number of electrons in
antibinding orbitals
Variation of orbital energies
2g < 1u
Heteronuclear diatomics
The bonding electron pair is shared unequally by two
atoms resulting Polar Bond. e.g: CO and HCl
LCAO gives
c A A cB B
with c A2 cB2
Polarity depends on
electronegativity ( )
For A B :
Relative Contribution of
c c (bonding),
2
A
2
B Atoms in a Polar Bond
c A2 cB2 (antibonding )
Heteronuclear diatomics
Pauling Electronegativity Scale:
A B 0.102 (E / kJ mol )
1 1/ 2