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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: σ bond
• Nitrogen 2px and
2py orbitals
No cylindrical
symmetry: π 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 σ
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 σ bonds with hybrid orbital of another C or H1s.
• Two π 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 (σ)
• Higher energy antibonding orbital (σ*)
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 Ψ when it
is inverted through
center of inversion.
• identical sign of Ψ
around center of
molecule (Gerade Opposite Sign, Ungerade Symmetry)
Symmetry)
• Opposite sign of Ψ,
(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
1σg2 1σu*21πu42σg2
• Bond Order
b= (½)(n-n*) (For N2 , b=3)
n=number of electrons in
bonding orbitals
n*=number of electrons in
antibinding orbitals
Variation of orbital energies
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 )
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