Take home quiz Consider the following ACln species: SCl2, OCl2, PCl3, SiCl4, SiCl621) Determine the

EGG and MGG of each compound 2) Arrange the compounds in decreasing Cl-A-Cl bond angles 3) Are all the molecules polar? Give the list of all the polar compounds from the given 4) Identify the orbitals involved in the bond A-Cl

Answers SCl2

sp3-p

EGG: Tetrahedral MGG: Bent Angle Cl-S-Cl: < 109.5

Polar

OCl2 sp3-p
EGG: Tetrahedral MGG: Bent Angle Cl-O-Cl: < 109.5 Polar

Answers PCl3 sp3-p

EGG: Tetrahedral MGG: Trigonal pyramidal Angle Cl-P-Cl: < 109.5

Polar

SiCl4 sp3-p
EGG: Tetrahedral MGG: Tetrahedral Angle Cl-Si-Cl: 109.5 Nonpolar

Answers

SiCl622EGG: Octahedral MGG: Octahedral

Angle Cl-Si-Cl: 180, 90

Nonpolar

sp3d2 -p

Answers
2) Arrange the compounds in decreasing Cl-A-Cl bond angles

Cl-Si-Cl > Cl-P-Cl > Cl-S-Cl = Cl-O-Cl SiCl4 > PCl3 > SCl2 = OCl2

Review
1. What are the two types of covalent bonding? 2. Explain how these two types of bond formed. 3. What is the shape of SeF4-molecule? 4. What are the orbital F overlaps involved in the bonding of Se?

Se F

Review
5. How many bonds are present in the molecule _____? 6. What are the orbital overlaps involved in the bonding of _____?

GENERAL CHEMISTRY

MOLECULAR ORBITALS
LECTURE

11

Scope
1. Molecular Orbitals 2. Molecular Orbital Energy Level Diagrams
i. ii. Homonuclear Diatomic Molecules Heteronuclear Diatomic Molecules

3. Bond Order and Bond Stability

Molecular Orbital Theory

Atomic orbitals on different atoms combined to form molecular orbitals (MOs).

Electron orbitals delocalized over the entire molecule Waves that describe atomic orbitals have both positive and negative amplitudes. As MOs are formed the phases can interact constructively or destructively.

Molecular Orbitals
There are two simple types of molecular orbitals that can be produced by the overlap of atomic orbitals.
1. (sigma) orbitals: head-on overlap of atomic orbitals 2. (pi) orbitals: side-on overlap of atomic orbitals

Molecular Orbitals: s orbital

Two 1s atomic orbitals that overlap produce two molecular orbitals designated as:
1. 1s or bonding molecular orbital 2. *1s or antibonding molecular orbital.

Molecular Orbitals: s orbital

Energetically, the molecular orbitals split.
1. The 1s lies lower in energy. 2. The *1s is higher in energy.

Molecular Orbitals: p orbital

The head-on overlap of two corresponding p atomic orbitals on different atoms, say 2px with 2px produces: 1. 2px bonding orbital * 2. 2px antibonding orbital

Molecular Orbitals: p orbital

Side overlap of two corresponding p atomic orbitals on different atoms (say 2py with 2py or 2pz with 2pz) produces: 1. 2py or 2pz (both are bonding orbitals)
2.

2py

or

2pz

(both are nonbonding orbitals)

Molecular Orbitals
How are the orbitals filled with electrons? Order of filling of MOs obeys same rules as for atomic orbitals: Aufbau principle Hunds Rule

Molecular Orbital Energy Level Diagram

Molecular hydrogen, H2 H: 1s1

*1s
1s

1s
2 H2: 1s

1s
AO of H
MO of H2

AO of H

*2s
2s
2s

MO Diagram of Li2
Li: 1s22s1

2s
*1s
1s AO of Li 1s

Li2: 21s *21s 22s

1s
MO of Li2

AO of Li

*2s
2s
2s

MO Diagram of Be2
Be: 1s22s2

2s
*1s
1s AO of Be 1s

Be2: 21s *21s 22s *22s

1s
MO of Be2

AO of Be

* 2 p *2p *2p

MO Diagram of O2
O: 1s22s22p4
2p

2p

2p 2p

O2: 21s *21s 22s *22s 22p 22p 22p *12p *12p
2 p

*2s
2s
AO of O

*1s
2s 1s 1s

2s
MO of O2

AO Of O

1s

* 2 p *2p *2p

MO Diagram of O22p

2p

2p 2p

O2-: 21s *21s 22s *22s 22p 22p 22p *22p *12p

2 p

*2s
2s
AO of O

*1s
2s 1s 1s

2s
MO of O2

1s
AO Of O

* 2 p *2p *2p

MO Diagram of O2+
2p

2p

2p 2p

O2+: 21s *21s 22s *22s 22p 22p 22p *12p

2 p

*2s
2s
AO of O

*1s
2s 1s 1s

2s
MO of O2

1s
AO Of O

O2

*2 p
*2p *2p

O22p

*2p *2p *2p

2p

2p 2p

2p

2p 2p

2p

2p

2p

*2s
2s 2s 2s

*2s
2s

2s
AO of O MO of O2 AO Of O

2s
AO of O MO of O2 AO Of O

O2

*2 p
*2p *2p

O2+
2p

*2p *2p *2p

2p

2p 2p

2p

2p 2p

2p

2p

2p

*2s
2s 2s 2s

*2s
2s

2s
AO of O MO of O2 AO Of O

2s
AO of O MO of O2 AO Of O

Exercise No.2

Draw the MO diagram of N2, N2- and N2+.

* 2 p *2p *2p

MO Diagram of N2N: 1s22s22p3

2p

2p
2 p 2p 2p

N2-: 21s *21s 22s *22s 22p 22p22p *12p

*1s
2s 1s 1s

*2s
2s
AO of O

2s
MO of O2

1s
AO Of O

N2-

* 2 p
*2p *2p

O22p

*2p *2p *2p

2p
2p

2p

2p 2p

2p

2p 2p

2p

*2s
2s
AO Of N

*2s
2s 2s 2s

2s
MO of N2

2s
AO Of N AO of O MO of O2 AO Of O

Bond Order and Bond Stability

The stability of a bond is described by its bond order

# e in bonding orbitals # e in antibondin g orbitals bo =

-

The larger the bond order, the more stable the molecule or ion is. The greater the bond order, the shorter the bond length and the greater the bond energy

Magnetic Properties
Diamagnetic
all electrons are paired

Paramagnetic
presence of unpaired electron (s)

Bond Order of H2
*1s
1s 1s

H2: 21s

Bo = (2-0) = 1
Diamagnetic

1s
AO of H
MO of H2

AO of H

*2s
2s
2s

Bond Order of Li2

Li2: 21s *21s 22s Bo = (4-2) = 1
Diamagnetic

2s
*1s
1s AO of Li 1s

1s
MO of Li2

AO of Li

*2s
2s
2s

Bond Order of Be2

Be2: 21s *21s 22s *22s Bo = (4-4) = 0
-Be is stable as an atom
1s

2s
*1s
1s AO of Be

Diamagnetic

1s
MO of Be2

AO Of Be

* 2 p *2p *2p

Bond Order of O2
2p

2p

2p 2p

O2: 21s *21s 22s *22s 22p 22p 22p *12p *12p

Bo = (10-6) = 2
2 p

Paramagnetic
*1s
2s 1s 1s

*2s
2s
AO of O

2s
MO of O2

AO Of O

1s

* 2 p *2p *2p

Bond Order of O22p

2p

2p 2p

O2-: 21s *21s 22s *22s 22p 22p 22p *22p *12p

Bo = (10-7) = 1.5
2 p

Paramagnetic
*1s
2s 1s 1s

*2s
2s
AO of O

2s
MO of O2

AO Of O

1s

* 2 p *2p *2p

Bond Order of O2+

2p

2p

2p 2p

O2+: 21s *21s 22s *22s 22p 22p 22p *12p

Bo = (10-5) = 2.5
2 p

Paramagnetic
*1s
2s 1s 1s

*2s
2s
AO of O

2s
MO of O2

AO Of O

1s

Bond Order and Bond Stability

O2 Bo =2 O2- Bo =1.5 O2+ Bo =2.5

Bond Length: O2- > O2 > O2+ Bond Energy: O2+ > O2 > O2O2+ > O2 > O2Stability:

* 2 p *2p *2p

Bond Order of N22p

2p
2p 2p 2p

N2-: 21s *21s 22s *22s 22p 22p22p *12p

Bo = (10-5) = 2.5
Paramagnetic
*1s
2s 1s 1s

*2s
2s
AO Of N

2s
MO of N2

AO Of N

1s

Heteronuclear Diatomic Molecule

Atomic orbitals of more electronegative element are lower in energy than the corresponding orbitals of less electronegative element The closer the energy of MO is to the energy of one of the AO the more of the character of that AO it shows

Quiz 12 (13/13)

May 8, 2013

1.Draw the MO diagram of F2 3 pts 2.Write the molecular orbital notation (electron configuration) of F2-, F2 and F2+. 6 pts 3.Calculate the bond order of each species. 3 pts 4. Which is the most stable compound? 1 pt