Molecular Orbital Theory

Combination of atomic orbitals on different atoms

(may be several) forms molecular orbitals (MO) (Valence bond theorycombination of atomic orbitals for same atom)

Electrons in MO belong to the molecule as a whole

Electron cloud distribution Bond energies Magnetic properties

Molecular Orbit Theory

Molecular Orbit Theory

Same bonding orbital as more detailed bonding orbital of first MO slide

1 node

No nodes

Start with 2 atomic orbitals; end with 2 molecular orbitals The greater the atomic orbital overlapthe stronger the bond

Energy


* 2p
y

*
2 px

* 2p

2p

2 px

2p

*
2s

2s

1*s

For H2 through N2
1s

H+ 2

Ground state

Bond order?

Bond order =

Number bonding e- Number antibonding e2

Single: 1 Double: 2 Triple: 3

H+ 2

Ground state Paramagnetic unpaired spins

Bond order?

H+ 2

Excited state

H+ 2
More highly excited state

H2

Bond order: 1 ? Diamagnetic no unpaired spins

He+ 2

Bond order: ? Paramagnetic

He2

Never observed.
If existed, diamagnetic

0 Bond order: ?

Li 2

Bond order: 1 Diamagnetic

Be2

Bond order: 0 Diamagnetic

B2

Bond order: 1 Paramagnetic

C2

Bond order: 2 Diamagnetic

N2

Bond order: 3 Diamagnetic

O2
Aside: VSEPR predicts diamagnetic

.. .. :O::O:

Bond order: 2 ? Paramagnetic

Liquid Oxygen

Energy

MOLECULAR ELECTRON CONFIGURATIONS

N2

O2

Bond order O2: 2 Bond order O2+: 2.5 Bond order O2-: 1.5

DIATOMIC HETERONUCLEAR MOLECULE

HF

2 =1 2

Sometimes the valence bond and molecular orbital models are combined. Sigma bonds are treated using valence bond theory. Pi bonds are treated using molecular orbital theory.
Benzene C6H6

H Hybridization for carbon single bonds (CC and CH)? sp2

 bonds in benzene
from C sp 2 orbitals and H 1s orbitals

Ground state molecular orbital How many electrons in this orbital? 2

BENZENE PI BOND ORDER (Number of nodes from top view)

* Number valence electrons in C6H6? 6x4 +6 = 30 Number electrons in bonds? 12x2 = 24

Number
electrons in bonds? 6 Bond order of e- is 3. Bond order of e- per CC bond is .

ENRICHMENT

Ozone, O3

MOLECULAR ORBITALS FOR OZONE

ENRICHMENT

NEED TO KNOW

2CO3

OPTIONAL EXAMPLE: DIATOMIC HETERONUCLEAR MOLECULE

CO

OPTIONAL EXAMPLE: MOLECULAR ORBITALS FOR TRIATOMIC BeH2

What about Be1s? is too small to overlap appreciably with it H1s. It remains localized on Be and is a nb orbital.

What about Be2px and Be2py? 2py 2pzthere orientation is such that there is little overlap with H1s. They remain localized on Be and are nb orbitals.

Energy

1s

nb

(no overlap)

Molecular orbital diagram of BeH2. Bond order for molecule is 2. Bond order each bond is 2/2 = 1.