Chemical Bonding Theories

VSPER is usually a satisfactory method for

predicting molecular geometry.

To understand bonding and electronic

structure, we need to use quantum mechanics

From quantum mechanics:

 Valence Bond Theory
 Molecular Orbital Theory
 Theories of Bonding
Valence Bond Theory (VB)
Electrons occupy overlapping
atomic orbitals in a bond. Orbitals
may be hybridized, but essentially
belong to one atom.

Molecular Orbital Theory (MO)

Atomic orbitals combine to form
new orbitals which are spread out
over the entire molecule. Electrons
are in orbitals which belong to the
molecule as a whole. (not
responsible for this theory)
 Valence Bond Theory
Electrons in molecules occupy atomic orbitals.
Covalent bonding results from the overlap of orbitals.
Electrons in covalent bond must have opposite spins
 Valence Bond Theory
Example #1: H(1s1) + H(1s1)  H2
 Valence Bond Theory
Example #2: F(1s22s22p5) + F(1s22s22p5)  F2
 Valence Bond Theory
Example #3: H(1s1) + F(1s22s22p5)  HF
 Important Features of
Valence Bond Theory:
1) Bond forms when singly occupied atomic
orbitals on 2 atoms overlap.

2) 2 electrons shared in overlap in an orbital

must have opposite spins.

3) Formation of a bond results in lower

potential energy for the system.
 What if Valence Bond Theory
Fails?
m Chloride, BeCl2

VSEPR linear
Cl Be Cl both bonds equivalent

But…
• No unpaired electrons

How is this possible when Be atom has

no unpaired electrons? Other explanation?
 Hybridization of Atomic
Orbitals
Explains bonding if VB Theory fails
– Experimental data (NMR and IR) show that
more bonds are present than predicted

Describes bonding that are obtained by taking

combinations of atomic orbitals of the isolated
atoms.
– Number of hybrid orbitals are equal to the
number of orbitals used
 Hybridization of
Atomic Orbitals
Atomic orbitals on atom mix to form hybrid orbitals.

No unpaired e–
available for bonding

Promotion of an e–
 Hybrid Orbitals
Two sp orbitals point in opposite directions

Forms
2 “sp”
hybrid
orbitals
 Hybrid Orbitals

For simplicity sake, the far right schematics are shown

 Hybrid Orbitals
Each Be sp orbital overlaps a Cl 3p orbital to yield BeCl2.
2Cl + Be BeCl2

sp hybridization
Explaining Bond Discepancies
Ex: Boron trifluoride, BF3
..
.. F ..
VSEPR • trigonal planar 1200
. . B .. • all bonds equivalent
.. .
.
F
.F. ..

But…

• only 1 unpaired electron

• 2 types of overlap with 2s and 2p

 Hybrid Orbitals
The three sp2 orbitals point to the corners of an equilateral
triangle.
 Hybrid Orbitals
Each B sp2 orbital overlaps a F 2p orbital to yield BF3.

3F + B BF3
2s2 2p5
Hybrid Orbitals

sp2 hybridization
 Valence Bond Theory
hane, CH4

• only 2 unpaired electrons

• 2 types of overlap with 2s and 2p

 Hybrid Orbitals
four sp3 hybrid orbitals point to corners of a tetrahedron.
Hybrid Orbitals
 Hybrid Orbitals
Each C 2sp3 orbital overlaps a H 1s orbital to yield CH4.

4H + C CH4
1s1
 Hybrid Orbitals
Expanded Octets
 Hybrid Orbitals

XeF4

5s2 5p6 5d0

sp3d2
 Types of Hybrid Orbitals

5 common types

 sp hybridization
 sp2 hybridization
 sp3 hybridization
 sp3d hybridization
 sp3d2 hybridization
Hybridization #s #p #d #
orbitals orbitals orbitals hybrid
orbitals
 Predicting Hybridization

Lewis Number of Type of

structure electron domains hybridization
What is hybridization and geometry (where
applicable) of center atom in the following?

SF4 CH3OH O2

4 bonds + lone pair C: 4 domains (sp3) 3 domains

5 domains O: 4 domains (sp3) sp2
sp3d linear
see saw shape
 Hybridization in Molecules
Containing Multiple Bonds
All bonds considered thus far have been single bonds,
also called sigma () bonds.

sigma () bond = a bond resulting from overlap of

two orbitals both symmetric about the axis joining the
two atoms = end-to-end overlap

If you look down the axis, the overlapping

orbitals have a circular shape.
 Hybridization and Multiple
Bonds
Double and triple bonds consist of both sigma () and pi ()
bonds.

pi () bond = a bond resulting from overlap of two

orbitals both perpendicular to the axis joining the
two atoms= sideways overlap

• sp2 hybridization leaves one p

orbital “unhybridized”

Ex:
 H- -H
Ex: Ethylene, C2H4 -C = C-
H H

Number of (both C) = 3 hybridization = sp2

Electron domains

Double bond = 1  bond + 1  bond

Ex: Acetylene, C2H2 H–CC–H
Number of (both C) = 2 hybridization = sp
electron domains

Triple bond = 1  bond + 2  bonds

 Exercise:How many pi bonds and sigma bonds are in
each of the following molecules? Describe the
hybridization of each C atom.

H H Cl H
Cl C Cl C C H3C C C C C H
H H H H
(a) (b) (c)
Exercise:How many pi bonds and sigma bonds are in
each of the following molecules? Describe the
hybridization of each C atom.

H 3 H sp2 Cl H sp2
sp
Cl C Cl C C H3C C C C C H
H sp2 H sp3 sp2 sp sp
H H

(a) (b) (c)

Ans:
(a) 4 sigma bonds
(b) 5 sigma bonds, 1 pi bond
(c) 10 sigma bonds, 3 pi bonds
Bonding Theories and Descriptions
of Molecules with Delocalized
Bonding
The sigma and pi bonds in the previous examples were
all localized bonds.
localized bonds = bonds in which the  and 
bonding electrons are associated with only two atoms.
Molecules for which resonance is necessary when
drawing Lewis structures, require delocalized
bonding when applying valence bond theory.
delocalized bonds = bonds in which the  bonding
electrons are associated with more than two atoms.

Examples: NO3–, CO32–, C6H6 , O3

 Delocalized Bonding
H

Example: benzene, C6H6 H C H second

12

C C
6

+ resonance
1 5

Carbon = 3 electron domains C C

H C H
2 4

structure
hybridization = sp2 H
 Chemists know….

UC Irvine Department of Che

mistry Video
Covalent Bonding Video

Video Link