Valence Bond Theory

and
Molecular Orbital Theory
 Shapes of Atomic Orbitals for Electrons
Four different kinds of orbitals for electrons
denoted s, p, d, and f
s and p orbitals most important in organic and
biological chemistry
s orbitals: spherical, nucleus at center
p orbitals: dumbbell-shaped, nucleus at middle
d orbitals: elongated dumbbell-shaped, nucleus at
center

2
The Nature of Chemical Bonds:
Covalent bond forms when two atoms approach each
other closely so that a singly occupied orbital on one
atom overlaps a singly occupied orbital on the other
atom
Two models to describe covalent bonding.

Valence bond theory, Molecular orbital theory

Central Themes of Valence Bond Theory
Basic Principle of Valence Bond Theory: a covalent
bond forms when the orbitals from two atoms
overlap and a pair of electrons occupies the region
between the nuclei.

1) Opposing spins of the electron pair. The

region of space formed by the overlapping
orbitals has a maximum capacity of two
electrons that must have opposite spins.
2) Maximum overlap of bonding orbitals. The
bond strength depends on the attraction of
nuclei for the shared electrons, so the greater
the orbital overlap, the stronger the bond.
Central Themes of Valence Bond Theory
3) Hybridization of atomic orbitals.

bonding in simple diatomic molecules:

Example1: HF (direct overlap of the s and p orbitals of
isolated ground state atoms).

Example 2: CH4 (4 hydrogen atoms are bonded to a

central carbon atom)- hybridization happens to obtain
the correct bond angles.

Pauling proposed that the valence atomic orbitals in

the molecule are different from those in the
isolated atoms. We call this Hybridization!
Fig. 11.1
What Is A Hybrid Orbital?

are a type of atomic orbital that results when two or more atomic orbitals
of an isolated atom mix (the number of hybrid orbitals on a covalently
bonded atom is equal to the number of atomic orbitals used to form the
hybrid orbitals)

are used to describe the orbitals in covalently bonded atoms (hybrid

orbitals do not exist in isolated atoms),

have shapes and orientations that are very different from those of atomic
orbitals in isolated atoms

in a set are equivalent, and form identical bonds (when the bonds are to a
set of identical atoms), and

are usually involved in sigma bonds in polyatomic molecules; pi bonds

usually involve the overlap of unhybridized orbitals.
In Hybridization there is mixing or
blending of atomic orbitals to
accommodate the spatial
requirements in a molecule.

Hybridization occurs to minimize

electron pair repulsions when atoms
are brought together to form
molecules.
 Types of Hybrid Orbitals

1. sp3 Orbitals and the Structure of Methane

Carbon has 4 valence electrons (2s2 2p2)
In CH4, all CH bonds are identical (tetrahedral)
sp3 hybrid orbitals: s orbital and three p orbitals
combine to form four equivalent, unsymmetrical,
tetrahedral orbitals (sppp = sp3), Pauling (1931)

11
Carbon: 2s22px12py1 one electron in each of four sp3
The Structure of Methane
sp3 orbitals on C overlap with 1s orbitals on 4 H atoms
to form four identical C-H bonds
Each CH bond has a strength of 436 (438) kJ/mol and
length of 109 pm
Bond angle: each HCH is 109.5, the tetrahedral
angle.

13
The sp3 Hybrid Orbitals in NH3 and H2O

Fig. 11.5
Hybridization of Nitrogen and Oxygen
Elements other than C can have hybridized orbitals
HNH bond angle in ammonia (NH3) 107.3
C-N-H bond angle is 110.3
Ns orbitals (sppp) hybridize to form four sp3 orbitals
One sp3 orbital is occupied by two nonbonding
electrons, and three sp3 orbitals have one electron each,
forming bonds to H and CH3.

15
sp3 Orbitals and the Structure of Ethane
Two Cs bond to each other by s overlap of an sp3
orbital from each
Three sp3 orbitals on each C overlap with H 1s orbitals
to form six CH bonds
CH bond strength in ethane 423 kJ/mol
CC bond is 154 pm long and strength is 376 kJ/mol
All bond angles of ethane are tetrahedral

16
2. sp2 Orbitals and the Structure of
Ethylene
sp2 hybrid orbitals: 2s orbital combines with two 2p
orbitals, giving 3 orbitals (spp = sp2). This results in a
double bond.
sp2 orbitals are in a plane with 120 angles
Remaining p orbital is perpendicular to the plane

17
Bonds From sp2 Hybrid Orbitals
Two sp2-hybridized orbitals overlap to form a s bond
p orbitals overlap side-to-side to formation a pi () bond
sp2sp2 s bond and 2p2p bond result in sharing four
electrons and formation of C-C double bond
Electrons in the s bond are centered between nuclei
Electrons in the bond occupy regions are on either side of a
line between nuclei

18
Structure of Ethylene
H atoms form s bonds with four sp2 orbitals
HCH and HCC bond angles of about 120
CC double bond in ethylene shorter and stronger than
single bond in ethane
Ethylene C=C bond length 134 pm (CC 154 pm)

19
Fig. 11.3
3. sp Orbitals and the Structure of Acetylene
C-C a triple bond sharing six electrons
Carbon 2s orbital hybridizes with a single p orbital
giving two sp hybrids
two p orbitals remain unchanged
sp orbitals are linear, 180 apart on x-axis
Two p orbitals are perpendicular on the y-axis and the
z-axis

21
Orbitals of Acetylene
Two sp hybrid orbitals from each C form spsp s bond
pz orbitals from each C form a pzpz bond by sideways
overlap and py orbitals overlap similarly

22
Bonding in Acetylene
Sharing of six electrons forms C C

Two sp orbitals form s bonds with hydrogens

23
 4. The sp3d Hybrid Orbitals in PCl5

Fig. 11.6
 5. The sp3d2 Hybrid Orbitals in SF6

Sulfur Hexafluoride -- SF6

Fig. 11.7
Molecular Orbital Theory
A molecular orbital (MO): where electrons are most likely
to be found (specific energy and general shape) in a molecule

Additive combination (bonding) MO is lower in energy

Subtractive combination (antibonding) MO is higher energy

27
Molecular Orbitals in Ethylene
The bonding MO is from combining p orbital lobes
with the same algebraic sign
The antibonding MO is from combining lobes with
opposite signs
Only bonding MO is occupied

28
Valence Bond Theory vs. MO
Theory
VB Theory begins with two steps:
hybridization (where necessary to get atomic orbitals that
point at each other)
combination of hybrid orbitals to make bonds with
electron density localized between the two bonding atoms

Key differences between MO and VB theory:

MO theory has electrons distributed over molecule
VB theory localizes an electron pair between two atoms

MO theory combines AOs on DIFFERENT atoms to make

MOs (LCAO)
VB theory combines AOs on the SAME atom to make
hybridized atomic orbitals (hybridization)

In MO theory, the symmetry (or antisymmetry) must be

retained in each orbital.
In VB theory, all orbitals must be looked at once to see
retention of the molecules symmetry. 29
Sigma and Pi Bonds
 Difference between sigma and pi bond
Sigma bond()
Formed by head to head overlap of AOs
The 2 AOs that overlap are symmetrical about the x axis
joining the 2 nuclei.
Has free rotation
Lower energy
Only one bond can exist between two atoms( a single
covalent bond)
Pi bond()
Formed by side-to-side overlap of AOs
No free rotation
Has higher energy
One or two bonds can exist between two atoms
Have nodal plane on the molecular axis and no longer
symmetrical about the molecular axis.
 Formation of Sigma Molecular Orbitals:
1. Overlapping of two 1s atomic orbital

Example: H2

+ bonding

antibonding

2. Overlapping of two px atomic orbital

bonding

antibonding
 +

3. Overlapping of an s and px atomic orbitals

bonding
+

antibonding

4. Overlapping of px and dz2 or dx2-y2

bonding

antibonding
 Formation of Pi Molecular Orbitals:
1. Overlapping of two py atomic orbitals

+ bonding

antibonding

2. Overlapping of two pz atomic orbitals

+ bonding

antibonding
3. Overlapping of py or pz with dxz or dxy

+ bonding

antibonding
Fig. 11.10
Fig. 11.11
Comparison between sigma and pi electrons in
ethylene and acetylene
1. Pi electron are made exposed to the environment
than the sigma electrons.
2. Pi electrons are more reactive than sigma electrons.
3. The looseness of the pi electrons in C2H2 is less than
in C2H4. This is the result of the greater s character in
sp hybrids as compared with the s character in sp2
hydrid.
4. Pi electrons in C2H2 are attracted more strongly
towards the nucleus than the pi electrons in C2H4.
5. The pi bonds in C2H2 are more susceptible to attack
by other chemical entities than in C2H4.
 Valence Bond Theory: Overlap of Atomic Orbitals

H-H s bond - overlap of s orbitals

1s
s bond - overlap of
H-F F: +
2p s orbital and p orbital
1 s bond - head/head
N2 N:
2s 2p overlap of p orbitals
Bonds with hybridization of atomic orbitals: 2 bonds - sidewise
overlap of p orbitals

sp3 hybridization
2s 2p
CH4 H: C:
1s sp3 C atom:
4 s bonds - overlap of
H-s orbitals and sp3 orbitals
Of C

A single sp3 orbital, each with single electron

sp2 hybridization
H
H2CO C: C atom
2s 2p 3 s bond;
H C O
1 bond
O

H H sp2 p
A single sp2 orbital, each with single electron

sp hybridization
C atom:
CO2 C:
2s 2p 2 s bonds
O
O C O
C O 2 bond
sp p
A single sp orbital, each with single electron
 Dinitrogren: 2 Models

N N
1 s bond - head/head
without hybridization with just p electrons
overlap of p orbitals
N2 N: 2 bonds - sidewise
2s 2p overlap of p orbitals
with sp hybridization with all valence electrons
2nd sp orbital
N2 N: 1st sp orbital
2s 2p one with 1 s bonds
nonbonded 2 bond
sp p N N
pair

O atom in H2CO (previous slide) O

H H

O:
2s 2p O atom
Can form 1 s bond;
sp2 p Can form 1 bond
Has 2 nonbonded pairs
-geometry around O is trigonal planar
- requires 3 equivalent orbitals from the O
- hence, sp2 hybridization