5.

61 2004 Lecture #34 page 1

BUILDING MOLECULES OUT OF MOLECULAR ORBITALS

HETERONUCLEAR DIATOMICS

If the atoms are similar, e.g. in molecules NO and CO, considerations are similar
Same MOs and energy ordering can be used

CO – isoelectronic with N 2 - has similar triple bond configuration

NO – has one additional electron in a π∗2px,y antibonding orbital

Bond order 2.5
Unpaired electron - paramagnetic
L = 1, M L = ±1, S = 1 2, M S = ± 1 2
2
Π "doublet pi" state

Generally MOs for heteronuclear diatomics must be formed from AOs of

unequal energies
−

E AOB

E
AO A

H AA − E H AB − SE
=0
H AB − SE H BB − E
Note H AA ≠ H BB
To a first approximation, neglect overlap between the orbitals (S = 0). Then

2 12
H AA + H BB ± ( H AA − H BB ) ⎡1 − 4 H AB ( H AA − H BB ) ⎤
2 2

E= ⎣ ⎦
2

H AB measures interaction between AOs centered on different atoms

Small when energies are very different

In the limit H AB << ( H AA − H BB ) , E = H AA or H BB

5.61 2004 Lecture #34 page 2

Don't need to consider MOs constructed from AOs of very different energies

12
If H AB << ( H AA − H BB ) , then ⎡1 − 4 H AB ( H AA − H BB ) ⎤⎦ ≈ 1 − 2 H AB ( H AA − H BB )
2 2 2 2
⎣
2 2
H AB H AB
E1 ≈ H AA − E2 ≈ H BB +
H AA − H BB H AA − H BB

As before, describe molecular wavefunction through VB or MO approach

MO approach far more commonly used

Construct 1-electron MOs out of the AOs

ψ 1 = c1 A AOA + c1B AOB Bonding MO

If AOA energy is lower (H AA < H BB ), then c1 A > c1B

ψ 2 = c2 A AOA + c2 B AOB Antibonding MO

If AOA energy is lower (H AA < H BB ), then c1 A < c1B

Simplest MO treatment: put 2 electrons in lower MO

ψ el (1, 2 ) = ψ 1 (1)ψ 1 ( 2 ) = ⎡⎣ c1 A AOA (1) + c1B AOB (1) ⎤⎦ ⎡⎣c1 A AOA ( 2 ) + c1B AOB ( 2 ) ⎤⎦
= c12A AOA (1) AOA ( 2 ) + c1 Ac1B ⎡⎣ AOA (1) AOB ( 2 ) + AOB (1) AOA ( 2 ) ⎤⎦ + c12B AOB (1) AOB ( 2 )
"ionic" covalent "ionic"

Configuration interaction: include contribution from higher MO

ψ elCI (1, 2 ) = C1ψ 1 (1)ψ 1 ( 2 ) + C2ψ 2 (1)ψ 2 ( 2 )

Many more MOs could be included in ψ elCI

Instead of using AOs to construct the MOs, could use other functions
e.g. Gaussians which might approximate the AOs.

Variational optimization of the Gaussian or other functions, and the coefficients

Ci in ψ elCI
5.61 2004 Lecture #34 page 3

e.g. diatomic molecule AB, with B more electronegative than A

Molecule AB
Atom A Atom B
σ∗2p

π∗2p
2pA
2pB
σ2p

π2p

σ∗2s
2sA
2sB
σ2s

σ∗1s
1sA
1sB
σ1s

e.g. CO triple bond

Electron configuration KK ( 2 sσ ) ( 2 sσ *) ( 2 pπ ) ( 2 pσ )
2 2 4 2
5.61 2004 Lecture #34 page 4

Note no parity designations – no center of symmetry for inversion

Often MOs have contributions from various AOs (not just one AO on each atom)

In this case MOs can't be labeled by specific AOs

MOs can't be labeled as strictly "bonding" or "antibonding"
But σ, π symmetries still hold, so σ and π MOs are just numbered in order of
increasing energy

Electron configuration (1σ ) ( 2σ ) ( 3σ ) ( 4σ ) (1π ) ( 5σ )

2 2 2 2 4 2

Hartree-Fock self-consistent field (SCF) calculations of MOs based on LCAOs

AOs are described by H-like orbitals, or one or a sum of gaussians

or Slater-type orbitals (STOs) of form N nl r n −1e −ξ rYml (θ , φ )
e.g. C 2pz orbital involved in σ bonding described as sum of 3 STOs labeled 2pσ,
2pσ', 2pσ''

Initial level of MO description: each 1-electron MO is a linear combination of 2

AOs, one from each atom
Since AOs are written as sums of Slater-type orbitals, the MOs are also

Higher level of MO description: Each 1-electron MO is written as a linear

combination of more than 2 AOs, more than one from each atom

Table below: shows results of SCF LCAO MO calculation for CO

From W.M. Huo, J. Chem. Phys. 43, 624 (1965)

Each MO is a sum of many orbitals – all the coefficients > 0.1 are given
This defines the molecular wavefunction, which puts electrons into each MO
(Each MO energy in a.u. is given above the MO designation.)
5.61 2004 Lecture #34 page 5

-20.66 au -11.36 au -1.52 au -0.80 au -0.55 au

Carbon ξ 1σ 2σ 3σ 4σ 5σ
1s 5.37 -0.92 -0.12 -0.13 -0.11
1s’ 9.06 -0.08
2s 1.31 0.11 0.69
3s 2.96 0.20 0.27 0.21
2pσ 1.19 -0.22
2pσ’ 2.17 0.20 0.13 -0.33
2pσ’’ 5.82
Oxygen
1s 7.31 0.92 0.10
1s’ 11.8 0.08
2s 1.93 0.59 -0.43
3s 4.33 0.26 -0.14
2pσ 1.49 0.10 0.37 -0.21
2pσ’ 2.83 0.13 0.36 -0.18
2pσ’’ 5.90

-0.64 au
Carbon ξ 1π
2pπ 1.58 0.33
2pπ’ 3.34
Oxygen
2pπ 1.47 0.44
2pπ’ 2.85 0.38
2pπ’’ 5.78

Results:

1sσ electrons mostly on oxygen 1sσ = cC1σ 1sC + cO1σ 1sO

Non-bonding orbital cO1σ >> cC1σ

2σ electrons mostly on carbon 2σ = cC2σ 1sC + cO2σ 1sO

Non-bonding orbital cC2σ >> cO2σ
5.61 2004 Lecture #34 page 6

3σ electrons mostly on oxygen 3σ = cC3σ 2sC + cO3σ 2 sO

Lone pair (nonbonding) orbital cO3σ >> cC3σ

4σ electrons on both C and O 4σ = cC4σ2 s 2 sC + cO4σ2 s 2 sO ( + cC4σ3 s 3sC + cC4σ2 p 2 pC + cO4σ2 p 2 pO )

Bonding orbital (2 electrons) cO4σ ≈ cC4σ

1π electrons on both C and O 1π = cC1π 2 pC + cO1π 2 pO

Bonding orbital (4 electrons) cO1π ≈ cC1π

5σ electrons mostly on carbon 5σ = cC5σ 2 pC + cO5σ 2 pO

Non-bonding orbital cO5σ << cC5σ

Similar treatment for LiH or other simple hydrides

From B.J. Ransil, Rev. Mod. Phys. 32, 245 (1960).

-2.45 au -0.30 au
Lithium ξ 1σ 2σ
1s 2.70 0.99 0.13
2s 0.65 -0.32
2pσ 0.65 -0.23
Hydrogen
1s 1.00 0.38 -0.69

POLYATOMIC MOLECULES

Usually similar to diatomics because most bonding electrons are localized around
2 atoms

That's why e.g. C-H bond energies and bond lengths and vibrational frequencies
are similar even in very different molecules

e.g. H2S triatomic – water-like

5.61 2004 Lecture #34 page 7

H (1s )
S (1s 2 2 s 2 2 p 6 3s 2 3 p 4 )

On S atom, put 2 electrons in 3pz orbital, one electron on each of 3px and 3py
S atom can make 2 bonds with half-filled p orbitals

p orbitals are at 90˚ so the H-S-H bond angle should be 90˚

Experimental angle: 92˚

e.g. PH3 ammonia-like

H (1s )
P (1s 2 2 s 2 2 p 6 3s 2 3 p 3 )

P atom can make 3 bonds with half-filled p orbitals

H-P-H bond angles should be 90˚

Experimental angle 93˚

S P

1-electron MOs and molecular wavefunctions

For H2S, label the two H nuclei Hx, Hy

Form MOs from S 3px orbital and Hx 1s orbital, S 3py orbital and Hy 1s orbital
5.61 2004 Lecture #34 page 8

1-electron MOs:
φ x = a1sHx + b3 pxS φ y = a1sHy + b3 p yS a 2 + b 2 = 1 (normalization)

Molecular electronic configuration: 1sS2 2 sS2 2 pzS6 3sS2 3 pzS2 φ x2φ y2

Note that this shows which orbitals are occupied, but it is not the wavefunction
itself.

The wavefunction is the properly antisymmetrized combination. For H2O it would

be:

ψ (1, 2,...,10) =

⎡ 1sOα (1) 1sO β (1) 2 sOα (1) 2 sO β (1) 2 pxOα (1) 2 pxO β (1) φ xα (1) φ x β (1) φ yα (1) φ y β (1) ⎤
⎢ 1s α ( 2 ) " " φy β ( 2) ⎥
⎢ O ⎥
⎢ 1sOα ( 3 ) " " φ y β ( 3) ⎥
⎢ ⎥
⎢ 1sOα ( 4 ) φy β ( 4)
⎥
⎢ 1sOα ( 5 ) # # % # # φ y β ( 5) ⎥
⎢ ⎥
⎢ 1sOα ( 6 ) # # % # # φy β ( 6) ⎥
⎢ 1sOα ( 7 ) φy β (7) ⎥
⎢ ⎥
⎢ 1sOα ( 8 ) " " φ y β (8) ⎥
⎢ 1s α ( 9 ) " " φy β (9) ⎥
⎢ O ⎥
⎣⎢1sOα (10 ) 1sO β (10 ) 2 sOα (10 ) 2 sO β (10 ) 2 pxOα (10 ) 2 pxO β (10 ) φ xα (10 ) φ x β (10 ) φ y α (10 ) φ y β (10 ) ⎦⎥

PH3 is similar

H (1s )
P (1s 2 2 s 2 2 p 6 3s 2 3 p 3 )

Form MOs from P 3px orbital and Hx 1s orbital, P 3py orbital and Hy 1s orbital, P
3pz orbital and Hz 1s orbital

1-electron MOs:
φ x = a1sHx + b3 pxP φ y = a1sHy + b3 p yP φ z = a1sHz + b3 pzP a 2 + b 2 = 1 (normalization)
Molecular electronic configuration: 1sP2 2 sP2 2 pP6 3sP2 φ x2φ y2φ z2