Molecular Orbital Theory

Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

A Little Review

Molecular Orbitals

a bond forms
1s atomic orbital 1s atomic orbital sb molecular orbital
sigma s bonding molecular orbital

Molecular Orbitals

SIGMA BOND ()
A bond between two atoms in which the electron density of the molecular orbital is between the two nuclei is called a sigma bond. nuclei ( sb)2 molecular orbital

Molecular Orbital Theory

Orbitals Are Wave Functions

An s orbital value can either be less than zero or greater than zero. The two lobes of a p orbital are separated by a node and have opposite signs.

Orbitals Are Wave Functions

Sigma Bond Formation

Sigma Bonds
(zb)

Sigma Antibond Formation

Sigma Antibond Formation

z
(z*)

 indicates the most probable electron position is on the internuclear axis

Sigma Bonds
(zb) b indicates a bonding molecular orbital

z indicates the molecular orbital involves two pz atomic orbitals

(z*) * indicates an antibonding molecular orbital

Electrons in this orbital will weaken the bonds between these atoms.

Sigma Bonds
(sb)

z
(s*)

Pi Bond Formation
y

Pi Bond Formation
y y

 Antibond Formation
What is the symbol of a antibond? How is a antibond formed? What does a antibond look like?

Pi Antibond Formation
y y

Pi Bonds

y* y yb

yb

Pi Bonding Involving Px Orbitals

xb

Pi Bonding Involving Px Orbitals

x*

Pi Bonding Involving p Orbitals

px-px overlap gives xb and x* py-py overlap gives yb and y* 2p

xb xb

yb yb

Molecular Orbital Diagrams

Involving s and p Orbitals 2p energy

2s 1s

Molecular Orbital Diagrams

Involving s and p Orbitals 2p

Nonbonding molecular Antibonding Bonding molecular Sigma bonds and orbitals antibonds z 2 2

2s 1s

Diatomic Molecular Orbital Diagram

Strong pz-s interaction energy 2p
2 2 2 + + 2

2s 1s

Homonuclear Diatomic Molecules

Determine is the sequence of molecular orbitals based on the strong p z-s interaction diagram. Determine the bond order and magnetic properties for homodiatomic molecules of the first nine elements. Show the bond lengths are consistent with these diagrams.

Orbital Sequence (sn)(sb)(s*)(x,yb(zb)(x,y*)(z*) ) z* x,y* zb x,yb s* sb sn energy

2p

2s 1s

 )) Dinitrogen(12 total e Diberyllium(6 total ee ) Dicarbon(10 total Diboron (14 Dilithium (8

Complete the mo diagram for Li2Properties? 2 or N2 Bond Order and Magnetic , Be2, B2, C

2p energy

2s 1s

z* x,y* zb x,yb s* sb sn

Compare the bond order, bond length and magnetic properties of O2, O2+ , O2 and O22 z* x,y* 2p x,yb zb s* 2 + 2s b 2 s energy 1s n s

Dioxygen
O O

Compare the physical properties predicted for Dioxygen by the Lewis Dot Diagram and MO Theory

O O

Bond Order
Lewis Dot Structure Molecular Orbital Theory

2 2

Magnetic Properties ? (diamagnetic) paramagnetic 2 unpaired electrons

Compare the physical properties for the Dioxygenyl(I) Ion, Dioxygen, Superoxide Ion and Peroxide Ion Bond Length Bond Order 2.5 2 1.5 1 Magnetic Properties paramagnetic (1) paramagnetic (2) paramagnetic (1) diamagnetic

O2+ O2 O2 O22

1.123 1.207 1.26 1.49

Oxygen-Oxygen Bonds

O O

H O O H

Difluorine (18 total e) Dineon (20 total e)

Bond Order and Magnetic Properties?

2p

2s 1s

z* x,y* x,yb zb s* b s n s

energy

Homodiatomic Molecules
Electronic Configuration
H2 ( sb)2 He2 ( sb)2 ( s*)2 Li2 ( sn)4 ( sb)2 Be2 ( sn)4 ( sb)2 ( s*)2 bond bond length magnetic order properties () 1 0 1 0 2.67 diamagnetic 0.74 diamagnetic

1 B2 ( sn)4 ( sb)2 ( s*)2 ( xb)1 ( yb)1 1.59 paramagnetic

Homodiatomic Molecules
Electronic Configuration

C2 ( sn)4 (sb)2 (s*)2 ( x,yb)4 N2 ( sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 O2 ( sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x*)1 ( F2 ( sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x,y*)4 Ne2 ( sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x,y*)4

Homodiatomic Molecules
bond order C2 N2 O2 F2 Ne2 2 3 2 1 0 bond length () 1.31 1.10 1.207 1.42 magnetic properties
diamagnetic diamagnetic paramagnetic diamagnetic

Skeleton Diagram Failures

Carbon Monoxide
C O

or

C O

CO

+
+ +

+
-

+
+ -

+ ++ + + +

+ + - + +

+
-

- ++ -

- + - +

CO

+ +

+ -

Be

BeH2

2H

Nitrate Ion

O O N O

O O N O

O O N O

Nitrate Ion
O O N O
1.22

Nitrate Ion

2 z

O O N O

Nitrate Ion

O O N O

Nitrate Ion

O O N O

y
y

Nitrate Ion
y

Nitrate Ion
y

NO3

3O

NO3

3O

NO3

3O

CO