Chem 5

Chapter 12

Chemical Bonding II:

Additional Aspects

Part 2

November 22, 2002

 Summary of the Valence Bond Theory

• Hybridized orbitals are linear combinations of atomic orbitals of the central

atom, matching the molecular geometry predicted by VSEPR.
sp, sp2, sp3, sp3d, sp3d2

• A σ bond results from an end-to-end overlap of two atomic or hybrid orbitals.

• A π bond results from a side-to-side overlap of two p orbitals. It is a single
bond, with two electrons filling one π orbital.

In ethylene, the C=C double bond consists of a σ bond and a π bond.

Ethylene + +
+

H2C=CH2 _ _ _

In acetelyne, the C≡C triple bond consists of a σ bond and two π bonds.
 Sometimes, valence bond theory does not work:
.. ..
Lewis structure of O2 : O=O:

All electrons are paired.

So O2 is expected to be diamagnetic.

Demo O2 is paramagnetic.
Paramagnetic: There are unpaired electrons.

Diamagnetic: No unpaired electrons. N2 is diamagnetic.

 Robert S. Mulliken 1896 - 1986
Born in Newburyport, Massachusetts, Mulliken was the son of
an artist and a professor of organic chemistry at Massachusetts
Institute of Technology. Heavily influenced by his father’s work,
Mulliken developed an interest in chemistry as a boy, earning
his B.S. at M.I.T. in 1917, and his Ph.D. at the University of
Chicago in 1921.

Like Linus Pauling, Mulliken was exposed to the papers of G. N. Lewis and
Irving Langmuir on chemical bonding during his Ph.D. period. He traveled
extensively in Europe, meeting many prominent researchers. During a visit in
1925, he established a relationship with Friedrich Hund who helped him to
advance the molecular orbital theory. This work formed the basis of the research
that eventually earned him the Nobel Prize in Chemistry in 1966. However, it
was overshadowed for some time by the valence-bond method advocated by
Pauling.

Among the concepts introduced to chemists by Mulliken are molecular orbital,

electron donor and acceptor, and electron affinity. He is credited with helping to
provide a theoretical foundation for chemistry, which was primarily an empirical
science at the time.
 MOLECULAR ORBITAL THEORY
Basic idea: Electron density between atoms gives a chemical bond

• Linear combinations of atomic orbitals (AO) result in molecular orbitals (MO).

• The number of MOs is equal to the number of AOs combined.

• When two MOs are formed from two AOs, constructive interference gives a
bonding MO with a lower energy, and destructive interference gives an anti-
bonding MO with a higher energy than the original AOs.

• For MOs formed with equal energy AOs, the more nodes, the higher the
energy of the MO.

• Electrons fill MOs with the lowest energy first.

• Each orbital holds up to two electrons (Pauli exclusion principle)

and obeys Hund’s rule, just like atomic orbitals.
MOs Formed from Linear Combination of Two 1s AOs

1sA 1sB

A B
1sA + 1sB = MO1 1sA – 1sB = MO2
Constructive interference Destructive interference

B
A B A
Electron density builds Electron density
up between the atoms low in the middle
The two MOs
1sA – 1sB = MO2

+ -
Node

σ anti-bonding orbital Æ σ1s*

1sA + 1sB = MO1

σ bonding orbital Æ σ1s
 The Energy of the σ1s and σ1s* Orbitals
Energy higher than the original orbitals

σ1s*
1s orbital
1s orbital in A B in a free
E a free atom atom
σ1s

Energy lower than the original orbitals

The bonding in H2

H H2 H

σ1s*

E
1s 1s

σ1s

The electrons are placed in the σ1s.

The MO configuration of H2 is (σ1s)2.

H H2 H

σ1s*

E
1s 1s

σ1s

Two electrons in a bonding orbital

results in a stable molecule.
 He2

He He2 He

σ1s*
Atomic configuration
of He is 1s2
E
1s 1s

σ1s
One pair of electrons goes in σ1s
and the next pair in σ1s*
 MO configuration He2: (σ1s)2(σ1s*)2

He He2 He
σ1s*

E
1s 1s

σ1s
The bonding effect of the (σ1s)2 is cancelled by the
antibonding effect of (σ1s*)2. The He2 is not stable.
The MO configurations, such as He2:(σ1s)2(σ1s*)2,
tell us four things:

• Its shape, σ or π.

• The parent AOs.

• Its stability (bonding or antibonding):

Antibonding is designated with an asterisk (*).

• The number of electrons.

 BOND ORDER
A measure of bond strength and molecular stability.
If # of bonding electrons > # of antibonding electrons
then the molecule is stable.

Bond order = 1/2 { # of bonding –

electrons
# of antibonding
electrons }
For He2 (σ1s)2(σ1s*)2 BOND ORDER = 0

A high bond order indicates high bond energy and short

bond length.

Consider H2+,H2,He2+,He2...
First row diatomic molecules and ions
H2 H2+ He2+ He2

σ1s*
E
σ1s

Magnetism Dia- Para- Para- __

Bond order 1 ½ ½ 0

Bond energy
(kJ/mol) 436 225 251 —

Bond length
74 106 108 —
(pm)
Now look at second period homonuclear diatomic
σ * molecules
2s

Li2
2s 2s

E σ2s Fill the MO’s with

electrons, two in
σ1s* each MO from the
lowest energy level
1s 1s

σ1s
 Electron configuration for Li2
σ2s*

(σ1s)2(σ1s*)2(σ2s)2
2s
2s
Bond Order = (4 - 2)/2 =1
E σ2s
A stable single bond.
σ1s*
The σ1s and σ1s*
orbitals cancel.
1s 1s
We can omit the
inner shell.
σ1s
DIBERYLLIUM Be2

Be Be2 Be
σ2s*

E
2s 2s

σ2s

Fill the orbitals

Electron configuration for Be2 is (σ2s)2(σ2s*)2.

Be Be2 Be
σ2s* Bond Order
=(2 - 2)/2 =0
E
2s 2s

No bond
σ2s

How about B2? We need to use 2p orbitals to form MOs

because the Boron atoms have 2p electrons.
 Two 2px AOs σ2px & σ*2px MOs

σ*2px

+ - + - - +

Anti-bonding
- + - +
σ2px

_
- + --

Bonding
Two 2pz AOs π2pz & π*2pz MOs

+ -

_ π*2pz
+ +
- +
Anti-bonding
- - +
+
π2pz
-
Bonding
Two 2py AOs π2py & π*2py MOs

_ - +
+ -
π*2py
- - Anti-bonding
+ +
+

-
+
π2py
Bonding
 ENERGY LEVEL DIAGRAM
σ2p*
The π do not split as
π2p* much because of
weaker overlap.

π2p The π2px and π2py are

2p 2p degenerate
σ2p
We have not
E σ2s* considered
interactions between
2s 2s s and p orbitals,
which pushes the σ2p
σ2s up and σ∗2s down.
 MODIFIED ENERGY LEVEL DIAGRAM
σ2p*
π2p*
Notice that the σ2p and π2p
have switched !
σ2p
2p 2p
E π2p

σ2s*

2s 2s

σ2s
The Order of π2p and σ2p Changes for O, F and Ne
Li2 B2 C2 N2 O2 F2
σ2p*
E σ2p*
π2p*
π2p*
σ2p
2p 2p π2p
π2p 2p 2p
σ2p σ2p is more
Being away from the stable because
axis, π2p is more stable the larger Zeff
than σ2p , which is compensates
repelled by σ2s and σ2s* for the repulsion
σ2s* σ*2s. by σ2s and σ*2s.

2s 2s 2s 2s
σ2s σ2s
 Electron configuration for B2
σ2p*
π2p*
B is [He] 2s22p1

σ2p
2p 2p
E π2p
Fill electrons
σ2s* from 2s, 2p into
σ2s , σ2s* and π2p
2s 2s

σ2s
 Electron configuration for B2: Use HUND’s RULE
Unpaired electrons
σ2p* Paramagnetic!
π2p* Abbreviated configuration

(σ2s)2(σ2s*)2(π2p)2
σ2p
2p 2p
E π2p
Complete configuration
σ2s*
(σ1s)2(σ1s*)2(σ2s)2(σ2s*)2(π2p)2
2s 2s

σ2s Bond order = (4 - 2)/2 =1

Second row diatomic molecules
NOTE SWITCH
OF LABELS B2 C2 N2 O2 F2

σ2p*
π2p*
σ2p
E π2p
σ2s*
σ2s

Magnetism Para- Dia- Dia- Para- Dia-

Bond order 1 2 3 2 1

Bond E. (kJ/mol) 290 620 942 495 154

Bond length(pm) 159 131 110 121 143

 OXYGEN
Lewis Structure O O Expected to be
diamagnetic

σ2p* Bond Order = (6-2)/2 =2

π2p*
PARAMAGNETIC
E π2p
σ2p Consistent with the DEMO!
σ2s*
σ2s It was a triumph of MO
theory to explain the
paramagnetism of O2!
 OXYGEN
O O

What does the Lewis structure correspond to in a MO conf.?

σ2p* This MO configuration has all

π2p* electrons paired, but is higher in
energy according to Hund’s rule.
E π2p
σ2p
This excited state of O2 is diamagnetic,
σ2s* whereas the ground state of O2 is
σ2s paramagnetic.
Demo: Chemiluminascence of Singlet Oxygen

Such diamagnetic O2 in the excited state

can be generated in the following
chemical reaction, and emits light to
return to the paramagnetic ground state.
Cl2(aq) + H2O2 (aq) + 2OH- → O2*(g) + 2Cl- (aq) + 2H2O
Excited state
O2*(g) → O2(g) + hν