Heteroatomic molecular

orbitals
Heteroatomic molecular Carbon monoxide
orbitals
Physical Chemistry

Mix atomic orbitals
For discussion, treated
simplistically as one orbital
from each center
Lecture 25 Often close to correct
because a single orbital
Heteronuclear Diatomic Molecules predominates
Must mix orbitals of
Similar energy
Same symmetry
Molecular orbital energies
Rough estimation by
diagram
Calculated with computer
simulations

Example: carbon monoxide Example: carbon monoxide

Carbon monoxide
Atomic orbitals Hartree-Fock
2pC similar to 2pO calculations give 1 20.58 hartree
2sC similar to 2sO relative energies of
Allows an energy diagram
states 2 * 11.32 hartree
similar to homonuclear
diatomics Calculated with 3 1.55 hartree
Mixing occurs to create Gaussian
bonding and antibonding Not correct 4 * 0.79 hartree
states energies, but gives
Some mixing of 2s states
into the states from 2p
order of stability 1 0.64 hartree
Some mixing of 2p states Gives a filling order

into the states from 2s for producing 5 0.54 hartree
Produces a filling order for configurations
producing configurations

Determining configuration and

term of carbon monoxide Example 2: hydrogen fluoride
Fill MOs in order When atoms are of different energies, one must be
concerned with the relative energies and
Ground configuration symmetries of orbitals
(1)2(2*)2(3)2(4*)2(1)4(5)2 Orbitals of same symmetry and approximately similar
energy combine most effectively
Total angular momentum = 0 Can estimate approximate HF molecular orbitals
Total spin = 0 Energies calculated with Gaussian
Gives filling order of orbitals
Use term symbols as with 1 1sF 26.11 hartree
homonuclear diatomics 2 2sF

1.55 hartree
Note lack of indication of 1 3 C2 p0 F 1s H 0.71 hartree
inversion symmetry 1 2 p1F , 2 p1F 0.60 hartree
4 * D2 p0 F 1s H

1
Example 2: hydrogen fluoride Example 2: hydrogen fluoride
Finding ground configuration
Bond-order
10 electrons
Fill molecular orbitals in order 1 is a nonbonding orbital
2 is a nonbonding orbital
1 2 3 1
2 2 2 4

1 is a nonbonding orbital
Eigenvalues with respect to operations 3 is a bonding orbital
= 0 (all shells filled)

Consider only bonding and antibonding
S = 0 (all shells filled)
Even under reflection in vertical plane electrons
Term symbol 1
( 2 0) 1

BOHF
1 2

Example 3: hydrogen fluoride Example 4: Nitric oxide, NO

Excited configuration found by promoting a single
electron Fifteen (15) electrons
1 2 3 1 4
2 2 2 3 1 Use heteroatomic filling order
Eigenvalues of operators 1 2 2 2 3 2 1 4 4 2 (2 )3
Treat 3 electrons like 1 electron
The state of a hole is the state of an electron.
=1
Leads to term
S = 0, 1 (either paired or unpaired) S=
Terms that arise from this configuration Results ground-state term
1
3
2

Summary
Heteroatomic molecules are analyzed in a
manner similar to homoatomic molecules
Must know MOs
Must know filling order
MOs are more complex
Must involve atomic orbitals of similar energy and
symmetry
Energies calculated by computer
Hartree-Fock calculation relatively straightforward