BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 12

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Summary Lecture 11 -Molecular PE diagram

Born-Oppenheimer
Approximation
Assumed

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Summary Lecture 11
VB Theory: Bond regarded as being formed when electron in an
orbital on one atom pairs its spin with that of an electron in an
orbital on another atom;
Approximate Ground state Valence Bond wavefunction:
ΨA-B (1,2)=N {A(1)B(2) + B(1)A(2)} {  } ;
Sigma, pi, delta bonds;
Promotion and Hybridization;
n atomic orbitals of same centre gives n hybrid orbitals.
Ψ1 = C1,1 φ1 + C1,2 φ2 ………… + C1,nφn
………………………………………………………
………………………………………………………
Ψn = Cn,1 φ1 + Cn,2 φ2 ………… + Cn,nφn
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Summary Lecture 11
C1,1 , …….., Cn,n are determined so that directional properties of
resultant hybrid orbitals correspond to the shape of the molecule;
Ci,j2 is proportional to the contribution of the jth atomic orbital in
ith hybrid orbital.
sp hybrids : Ψ1 = φs + φ2pz ; Ψ2 = φs -φ2pz e.g. acetylene
sp2 hybrids : Ψ1 = s + 21/2px ; Ψ2 = s + (3/2)1/2px  (1/2)1/2py ;
e.g. ethylene. Ψ3 = s  (3/2)1/2px  (1/2)1/2py .
sp3 hybrids : Ψ1 = φ2s + φ2px + φ2py + φ2pz
e.g. methane Ψ2 = φ2s + φ2px - φ2py - φ2pz
Ψ3 = φ2s - φ2px - φ2py + φ2pz
Ψ4 = φ2s - φ2px + φ2py - φ2pz

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Summary Lecture 11 VBT–Hybridization Methane

High Energy (comp. to natural C) Higher Energy

This energy gain is compensated

by energy loss in better bond
formation.
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Summary Lecture 11
Resonance is the superposition of wave functions
 = covalent + ionic =  H-Cl (Cov)+ H+-Cl-
where λ2 is the relative proportion of ionic
contribution in the superposition;
Variation theorem: Energy of the trial wave
functions will always be higher than true energy
of the system ;
hence vary the  until the lowest possible energy
is reached.
Benzene:
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Summary Lecture 11 VBT– Hybridization & Resonance

Hybridization- Low energy atomic configuration

converted to produce high energy hybrid orbital
configuration.

Resonance hybrid – High energy molecular

structures’ wavefunctions combined to produce
the actual low energy molecular wave function.

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Molecular Orbital Theory
•An MO (MOLECULAR ORBITAL) gives through |Ψ2|,
the distribution of electron in a molecule.
•Spread throughout the molecule.

•Such a Ψ is complicated function; difficult to obtain

as a solution of SE. Approximation is needed.
•Many models are possible. (United atom method,
Linear Combination of Atomic Orbitals (LCAO) etc.)

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Molecular Orbital Theory

•Assume that MOs are linear combination of atomic

orbitals (LCAO-MO)

Ψ = Σi (Cii)
•N Atomic Orbitals() combined should give N MOs
(Ψ)

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Molecular Orbital Theory
•In a homonuclear diatomic species such as H2+
Ψ = CAA + CBB (The electron is either in A or B)

Since electron can be found with equal probability in

A or B, CA2 = CB2 Or CB = ± CA

•Possible wavefunctions for simple case H2+ as:

Ψ = N(A ± B)
•N is normalizing factor.
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Molecular Orbital Theory

Consider first: Ψ1 = N(A + B)

Born interpretation:
Probability density is proportional to the square of
modulus of wave function.

Ψ1 2 = N 2 (A 2 + B 2 + 2 A B)
Bonding MO (Energy is lowered for the
electron if it is placed in this orbital)
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Molecular Orbital Theory

Cylindrical symmetry around inter nuclear axis.

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Molecular Orbital Theory
Variation of bonding MO ψ1 along inter-nuclear axis

Ψ1 2 = N 2 (A 2 + 2 A B + B 2 )
•Lower energy;  orbital – resemblance with s orbital
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Molecular Orbital Theory
For H2+ We write the configuration as 1σ1

1σ because this is lower most energy in σ

type overlap.
Overlap Integral : S AB   A B d

S =1 perfect overlap and S= 0 no overlap.

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Molecular Orbital Theory

a: S ≈ 0 ; b: S >0 ; c: S = 0

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Molecular Orbital Theory

R R 2  ( R / a0 )
S HH  {1   2 }e
a0 3a0
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Molecular Orbital Theory
Now Consider : Ψ1 = N(A - B)

Born interpretation:

Ψ1 2 = N 2 (A 2 + B 2 - 2 A B)
Anti Bonding MO (Energy is raised for the
electron if it is placed in this orbital)

We write the configuration as 1σ*

σ * because this is excited state.
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Molecular Orbital Theory

Nodal Plane Exists

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Molecular Orbital Theory

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Molecular Orbital Theory
gerade and ungerade symbols (g,u) are
based on symmetry w.r.t. Centre of
Inversion.
Centre of Inversion: (x,y,z) and (-x,-y,-z)
have same properties
These symbols are not applicable for
molecules without centre of inversion such as
CO, Methane etc.

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Molecular Orbital Theory

Bonding Anti-bonding
(Even – g) (odd – u)

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Molecular Orbital Theory
Many electron Diatomic Molecules:
H2+ Molecular orbitals as basis.

1. Linear Combination of “suitable” valence

orbitals of atoms; N atomic orbitals should give
N Molecular orbitals.
2. Accommodate the electrons without violating
Pauli principle.
3. In degenerate orbitals, spin pairing should be
done after all such orbitals are singly occupied
with parallel spin (Hund’s rule).
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Molecular Orbital Theory

Inter nuclear Separation

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Molecular Orbital Theory

H2+ 1 1
g 106 pm ; 250 kJ/mol

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Molecular Orbital Theory

H2 1 2
g 74 pm ; 436 kJ/mol

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Molecular Orbital Theory

He2 1 g21 u2 does not exist. Anti bonding orbital

occupation is more destabilizing than the stabilizing effect
of bonding orbital occupation.
He2+ Exists. (spectroscopic evidence) Why?
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Molecular Orbital Theory
Consider O2 molecule; Consider only valence shell;

2s orbital combinations are same as 1s orbital

combinations; Consider 2p orbitals.

Anti-bonding
(odd – u)

Bonding
(even– g)

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Molecular Orbital Theory

Bonding Anti-bonding
(odd – u) (even– g)
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Molecular Orbital Theory (O2)

1 g21 u2 2 g21 u41 g2

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Molecular Orbital Theory
•We should have combined all σ type orbitals
together

Ψ = C1A2s + C2B2s + C3A2pz + C4Bpz

There is a mixing up of σ type orbitals. The effect is
seen in the N2 molecule.
Note that mixing happens when the mixing orbitals
are close by in energy.

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Molecular Orbital Theory (N2)

1 g21 u21 u4 2 g2

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Molecular Orbital Theory

Note: Upto N2
the 2σg is above
1πu

Be2 does not

exist; However,
Be metal exists.
(Band theory-
beyond this
course)

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Molecular Orbital Theory
(d orbital overlaps)

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Molecular Orbital Theory
Bond Order: ½ (N- N*)
N = No. Of Bonding electrons; N* = No. of antibonding electrons.

H2 : 1 g2 B.O. = ½ (2) =1

He2 : 1 12
g
2
u B.O. = ½ (2-2) =0

1 g21 u21 u4 2 g2
N2 : B.O. = ½ (8-2) =3

Bond order is an indicative number; not energy. So

while comparing be careful. Compare only that of
similar species such as O2 and O2+, but not O22+ and N2.

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Molecular Orbital Theory
Paramagnetism and diamagnetism:

Paramagnetic substances : Attracted towards

magnetic field. (unquenched spin or orbital mag.
Moment)

Diamagnetic substances: Repelled by a magnetic field.

Consider Oxygen molecule : 1 1 2 1 1

2
g
2
u
2
g
4
u
2
g

2 unpaired electrons; paramagnetic due unquenched

spin magnetic moment. Success of MO Theory

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