CH111_2024_SK_Lec_19

Molecular Electronic Structure
Bonding
What about H2 molecule?
r1A r1B
 ⎛ 2 1⎞ ⎛ 2 1 ⎞ 1 1 1 1
R H H 2 ~ ⎜ −∇1 − ⎟ + ⎜ −∇ 2 − ⎟ − − + +
⎝ r1A ⎠ ⎝ r2 B ⎠ r1B r2 A RAB r12
r12  1 1 1 1
r2A r2B H H2 = 
H H (1e) + 
H H (1e) − − + +
r1B r2 A RAB r12
Dihydrogen Molecule Can not be solved exactly à Approximate

(H2) 1
Place 2e with opp. spin in bonding orbital of H2 + jb1e = [1sA + 1sB ]
2(1 + S )
 1 
Space+Spin ϕ = ⎡ψ (1)ψ (2) ⎤ •  ⎡ α (1) β (2) − α (2) β (1) ⎤ 
bonding ⎣ b b ⎦   ⎣ ⎦ 
 2 
1
Spatial part! j H =
MO
[1sA (1) + 1sB (1)][1sA (2) + 1sB (2)]
2
2(1 + S )
1
jH2 =
MO
[1sA (1)1sA (2) + 1sB (1)1sB (2) + 1sA (1)1sB (2) + 1sB (1)1sA (2)]
2(1 + S )
MOT overemphasizes ionic terms in a covalent bond! VBT better?
Dihydrogen Molecule: One more
electron goes to bonding orbital
Bond strength increases: Bond order=1
Effective nuclear charge changes the absolute

Energy levels and the orbitals!
Matching of energies of AO important for LCAO-MO

If energies are not close to each other, they would
Not interact to form MOs.
Energies of H2+, H2, He2+, He2
He2+
He2
Matching of AO energies for MO
Z-axis
j± = c1y 1 ± c2y 2
S=0
PX/Y +s
PZ + s
Both symmetry and energy

S>0
matching is required for MO
Valence electrons are most important for bonding
• Due to large difference in energy of 1s(H) and 1s(F), LCAO-MO
for both 1S is not feasible in HF.
• Rather only 2Pz(F) [NOT 2Px/y(F)] and 1S(H) form a σ-bond.
The curious case of 2s-2s sigma
+ Bond length
bond… Bond length
H2 = 1.03 A0 = 2.62 A0
Li2
Li2
MO Contours show electron density maps
2s and 2s*
H2 Li2: core 1s
3s and 1p
Li2: core 1s* Li2: Valence 2s 1p*

Total
HOMO : Highest Occupied Molecular Orbital

Li2: Total O2 molecule
LUMO : Lowest Unoccupied Molecular Orbital
Expected MO and Energies for Dinitrogen
Is this a correct energy level diagram for N2?
There is a problem! Spectroscopy says NO!

Photoelectron spectra of Dinitrogen
Actual MO and Energy Diagram for N2
Nature 2004 vol 432 867
Mixing of 2S and 2P orbital occur because of small energy

gap between them. 2s and 2p electrons feels not so
different effective nuclear charge.
S-P Mixing in Atomic Orbitals
C1 and C2 not equal –
y ±SPz = c1y 2 s ± c2y 2 pz In the mix orbital:
S and PZ à different
Contributions in mix
2S and 2P AOs MIX due to less energy gap à 2s and 2p e feels

not so different Zeff. à Mixed states can form MOs
s-p Mixing: B2 magnetism confirms it!
Incorrect!
Boron is paramagnetic. This can only happen if the two electrons with
parallel spin are in the p-orbitals à p-bonding energies lower than s*?
MO Energy Diagram for F2
Less mixing of S and P orbital because of higher energy

Gap between 2S and 2P levels in Oxygen and Fluorine!
2s and 2p electrons feels very different nuclear charge
MO Energy Diagram (Homo-Diatomics)
Bond Order = ½ (# of bonding electrons - # of antibonding electrons)

Bond order = 0 à molecule can not exist – No bond formation
Bond order higher à stronger bond, shorter bond length
Bond order, strength, length...
...magnetism can be explained
Paired Spins: Diamagnetic

Unpaired spins: Paramagnetic
Hetero-nuclear Diatomics: HF
Electronegativity of F
much more than H
(as Zeff >> H):
Electrostatic potentials
can be computed which
gives a realistic picture
of the electron densities
in HF: “Egg” Shaped
Hetero-nuclear Diatomics: HCl
For Cl à 3p states close in energy to the 1s of H
Similar to HF, expect for

2p and 3p difference.
Can not tell where absolute

Energy levels will be unless
Spectroscopic evidences
exists. Or do QM calculations
Hetero-nuclear Diatomics: HBr
For Brà 4p states close in energy to the 1s of H!
Actually the 4p is higher in energy as opposed to
That of F(2p) and Cl(3p)
Take home messages
✪We can extend the knowledge of constructing H2+ molecular
orbital to develop molecular orbital’s for other homo or
hetero diatomic molecules
✪Things we should keep in mind:
Effective nuclear charge will change as we move on to

higher diatomic molecule
Symmetries and Energies of the atomic orbital’s must

match to form a molecular orbital
Valence electrons are the most important for bonding
S-p mixing can happen till N2 molecule, in general all the

atomic orbital can mix if it is symmetry allowed and they
are not well separated in terms of energy
What about more complex molecules?
Hybridization and Geometry

Hybrids: Linear Combination of S
and P leads to lowering of energy
Hybrid Orbital’s
• Linear combination of atomic orbital’s
within an atom leading to more effective
bonding situation
Free atom Atom in a field along z direction
2px 2py 2pz 2px 2py

Energy
sp sp
Linus Pauling, ~1930 2s
•Hybridization is close to VBT. Use of experimental information

•All hybrid orbitals equivalent and are orthonormal to each other
Linear Environment: s & 1-p mix: sp
2 equivalent hybrid orbitals of the same
energy and shape (directions different) j = c1y s + c2y p
sp
h1
S and P orbital of the j = c1y s - c2y p

sp
h2
Same atom! This is not
The same as S (overlap)
1 1
j =
sp
h1 ys + yp
2 2
1 1
jh 2 =
sp
ys - yp
2 2
Linear geometry with
Hybridized atom at the center 2S- and 2P- (similar energy)
Mixes to form hybrid orbital
which forms a MO with H (1S)
Contribution from s=0.5; contribution from p=0.5
Have to normalize each hybridized orbital Problem!!
Revisiting the 2s and 2p Ao’s wave functions
2s 2pz
Revisiting the 2s and 2p Ao’s wave functions
2s 2s
2pz
2s 2s 2pz
2pz 2s
Contours & bonding of sp-hybridization
2 more p-orbital available for bonding

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Molecular Electronic Structure

Dihydrogen Molecule Can not be solved exactly à Approximate

Bond strength increases: Bond order=1

Effective nuclear charge changes the absolute

Matching of energies of AO important for LCAO-MO

Both symmetry and energy

Li2: core 1s* Li2: Valence 2s 1p*

HOMO : Highest Occupied Molecular Orbital

There is a problem! Spectroscopy says NO!

Mixing of 2S and 2P orbital occur because of small energy

2S and 2P AOs MIX due to less energy gap à 2s and 2p e feels

Less mixing of S and P orbital because of higher energy

Bond Order = ½ (# of bonding electrons - # of antibonding electrons)

Paired Spins: Diamagnetic

Similar to HF, expect for

Can not tell where absolute

Effective nuclear charge will change as we move on to

Symmetries and Energies of the atomic orbital’s must

Valence electrons are the most important for bonding

S-p mixing can happen till N2 molecule, in general all the

Hybridization and Geometry

Free atom Atom in a field along z direction

2px 2py 2pz 2px 2py

•Hybridization is close to VBT. Use of experimental information

S and P orbital of the j = c1y s - c2y p

2 more p-orbital available for bonding

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