Topics :

Lewis Structures
Resonance
Formal Changes
VSEPR Theory
Hybridization
VBT
MOT

Molecular Structure &

Bonding
A molecular structure, unlike a simple
molecular formula, indicates the
exact 3-D nature of the molecule. It
indicates which atoms are bonded to
which atoms, and the 3-D orientation
of those atoms relative to each other.

Molecular Formula vs.

Molecular Structure
Molecular formula H2O
Molecular structure:
.. ..

O
H

Molecular Structure
Two issues:
What is stuck to what?
How are they oriented?

What is stuck to what?

The first thing you need to do in drawing a
molecular structure is to figure out which atom
sticks to which other atoms to generate a
skeletal model of the molecule.
The skeletal model is called a Lewis Dot Structure.

Lewis Dot Structures

The first step towards establishing the
full 3-D geometry of a molecule is
determining what is stuck to what
and how each atom is connected.
Lewis Dot Structures provide this
information.

Two Rules
1.

2.

Total # of valence electrons the

total number of valence electrons
must be accounted for, no extras,
none missing.
Octet Rule every atom should
have an octet (8) electrons
associated with it. Hydrogen
should only have 2 (a duet).

Determining the number

of valence electrons:
Full d-orbitals do not count as valence
electrons. They belong to the inner shell.
For example:
As is [Ar]4s23d104p3
This is FIVE (5) valence electrons. The 3d
is part of the inner shell (n=3) which is
full.

Total Number of Valence

Electrons
The total number of available valence
electrons is just the sum of the number of
valence electrons that each atom
possesses (ignoring d-orbital electrons)
So, for H2O, the total number of valence
electrons = 2 x 1 (each H is 1s1) + 6 (O is
2s22p4) = 8
CO2 has a total number of valence electrons
= 4 (C is 2s22p2) + 2 * 6 (O is 2s22p4) = 16

Central Atom
In a molecule, there are only 2 types of atoms:
1.

2.

central bonded to more than one other

atom.
terminal bonded to only one other
atom.

You can have more than one central atom in a

molecule.

How many central atoms

in ethanol?
A.
B.
C.
D.
E.

1
2
3
4
5

Bonds
Bonds are pairs of shared electrons.
Each bond has 2 electrons in it.
You can have multiple bonds between the same 2
atoms. For example:
C-O
C=O
C
O
Each of the lines represents 1 bond with 2
electrons in it.

Lewis Dot Structure

Each electron is represented by a dot in
the structure
.

:Cl:

That symbol with the dots indicate a

chlorine atom with 7 valence
electrons.

Drawing Lewis Dot

Structures
1.

2.

3.

Determine the total number of

valence electrons.
Determine which atom is the
central atom.
Stick everything to the central
atom using a single bond.

Dot structure for H2O

1. Total number of valence electrons:

6 + (2 x 1) =8
2. Central Atom typically, the central atom
will be left most and/or bottom most in
the periodic table. It is the atom that
wants more than one thing stuck to it. H
is NEVER the central atom.
3. Stick all terminal atoms to the central
atom using a single bond.

Dot structure for H2O

HOH
Drawing Lewis Dot Structures
Determine the total number of valence
electrons.
2. Determine which atom is the central atom.
3. Stick everything to the central atom using a
single bond.
4. Fill the octet of every atom by adding dots.
5. Verify the total number of valence electrons in
the structure.
1.

Dot structure for H2O

..

HOH

That is a total of 8 valence electrons

used: each bond is 2, and there are 2
non-bonding pairs.

Drawing Lewis Dot

Structures
1.
2.
3.
4.
5.
6.

7.

Determine the total number of valence

electrons.
Determine which atom is the central atom.
Stick everything to the central atom using a
single bond.
Fill the octet of every atom by adding dots.
Verify the total number of valence electrons in
the structure.
Add or subtract electrons to the structure by
making/breaking bonds to get the correct # of
valence electrons.
Check the formal charge of each atom.

Formal Charge of an
atom
Formal charge isnt a real charge. Its a pseudocharge on a single atom.
Formal charge = number of valence electrons
number of bonds number of non-bonding
electrons.
Formal charge (FC) is ideally 0, acceptably +/-1, on
occasion +/- 2. The more 0s in a structure, the
better.
The total of all the formal charges of each atom will
always equal the charge on the entire structure (0
for neutral molecules).

Dot structure for H2O

..

HOH

FC (H) = 1-1-0 = 0
FC (O) = 6 2 4 = 0
This is excellent, all the FCs are 0!

Another example
Lets try CO2
Drawing Lewis Dot Structures
1.
2.
3.
4.
5.
6.

7.

Determine the total number of valence electrons.

Determine which atom is the central atom.
Stick everything to the central atom using a single bond.
Fill the octet of every atom by adding dots.
Verify the total number of valence electrons in the structure.
Add or subtract electrons to the structure by
making/breaking bonds to get the correct # of valence
electrons.
Check the formal charge of each atom.

CO2
CO2
Total number of valence electrons = 4 from
carbon + 2x6 from oxygen = 16
Central Atom?
Either C or O could be a central atom. C is
more likely (to the left, to the left, to the
left)

CO2
CO2
16 total valence electrons
OCO
Fill out the octets
..

..

..

:O C - O:

CO2
16 total valence electrons
..

..

..

:O C - O:

Structure has 20 electrons in it. Too many!
I need to lose 4 electrons. Whats the best way to
do that?
Make 2 bonds each new bond costs 2 electrons

CO2
:O = C = O:

Structure has 16 electrons in it. Just right!

Notice, this works because there are 2 ways
to count the electrons:
1. When I count the total # of electrons, I
count each electron once.
2. When I count the electrons for each
atom, I count the bond twice (once for
each atom in the bond)

CO2
:O = C = O:

Is this the only structure I could have drawn?

I only needed two new bonds, I didnt specify
where they needed to go!
..
:O
C - O:

..
:O - C
O:

Which is correct?

Choosing between different

structures?
The first test is formal charge:
:O = C = O:

FC (O) = 6 2 4 = 0
FC (C) = 4 4 0 = 0
..
:O
C - O:

FC (left O) = 6 3 2 = 1
FC (C) = 4 4 0 = 0
FC (right O) = 6 1 6 = -1
Based on formal charge the upper structure is the
better one.

Are these even different?

:O

..
C - O:

..
:O - C O:

Depends on what I mean by different!

Are they different?

:O1

..
C O2 :

..
:O1 - C O2 :

If I label them, I can see a difference. (Isotopic

labeling).
If I dont label them, they are interchangeable,
just rotate the top one to get the bottom one.

Exceptions to the Octet

Rule
There are exceptions to the octet rule:
1.

2.

Incomplete octets less than 8

electrons.
Expanded octets more than 8
electrons

Incomplete Octets
The most common elements that show incomplete
octets are B, Be besides H.
So, for example, BCl3 has the Lewis structure:
..
..
: Cl B Cl:

: Cl :

Total valence electrons is correct at 24.

FC (B) = 3 - 3 0 = 0
FC (Cl) = 7- 1 - 6 = 0

Expanded Octets
The most common atoms to show expanded octets are
P and S. It is also possible for some transition
metals.
An example of an expanded octet would be PCl 5:
..
..
:Cl: :Cl:
Total valence e - = 40
..
..
:Cl P - Cl :
FC(P) = 5 5 0 =0

: Cl:
FC (Cl) = 7 1 6 = 0

Resonance
Some molecules may have more than
one valid Lewis structure. These
structures differ in the placement of
multiple bonds.
In molecules with resonance, none of
the Lewis structures accurately
represents the true bonding in the
molecule.

Resonance
The molecule SO2 has two
resonance structures:

: :
:
: :

: :
:
: :

[ O=S-O: ] [ :O-S=O]
The molecule has two equivalent
bonds between sulfur and oxygen.

Resonance
The sulfur-oxygen bonds are identicallonger than double bonds, and shorter
than single bonds.

: :

: :

: :

: :

[ O=S-O: ] [ :O-S=O]
The true structure of the molecule is in
between the two Lewis structures
drawn.

Resonance
The Lewis structure and VSEPR theory
correctly predict the shape, polarity and
bond angles (120o) of the molecule.
However, this approach cannot
accurately predict the identical nature
of the bonds. The sulfur oxygen bonds
are equivalent, and somewhat shorter
than single bonds, and slightly longer
than double bonds.

Formal Charges
Formal charge is a way to keep
track of the electrons in a covalent
molecule. The formal charges can
also be used to determine if one
Lewis structure is more valid than
another.

Formal Charges
The formal charge on an atom is a
comparison between the number of
valence electrons on each atom and
the number of electrons it has in the
Lewis structure.

Formal Charges
Consider the ion SCN-1. There are
three valid Lewis structures for the ion.
1

: :

: :

[:S=C=N:] [:S-C N:] [:S C-N:]

Formal charges can be used to
determine the major contributor(s) to
the actual structure of the ion.

Formal Charges
Divide the bonds in half and
determine the number of electrons
on each atom.
1

: :

: :

[:S=C=N:] [:S-C N:] [:S C-N:]

6e 4e 6e

7e 4e 5e 5e 4e 7e

Formal Charges
Compare the number of electrons in
the structure to the number of valence
electrons.
1

: :

: :

[:S=C=N:] [:S-C N:] [:S C-N:]

6e 4e 6e
6e 4e 5e

7e 4e 5e 5e 4e 7e
6e 4e 5e 6e 4e 5e

Formal Charges
The net charge is the formal charge
on each atom.
0

-1

-1 0
1

+1

0 -2
1

6e
5e

7e
6e

4e
4e

5e
5e

5e
6e

: :

4e
4e

: :

6e
6e

[:S=C=N:] [:S-C N:] [:S C-N:]

4e
4e

7e
5e

Formal Charges
The net charge is the formal
charge on each atom.
0

-1

-1 0
1

: :

: :

0
0 -2

+1

[:S=C=N:] [:S-C N:] [:S C-N:]

The sum of the formal charges
must equal the charge on the ion.

Formal Charges
There are two rules used to determine
the most likely Lewis structure(s).
1. Atoms try to achieve formal
charges as close to zero as
possible.
2. Any negative formal charges
should reside on the most
electronegative atoms.

Formal Charges
The third Lewis structure is unlikely,
due to the high formal charge on
nitrogen.
-1 0

0
1

+1

: :

: :

-1

0
-2
1

[:S=C=N:] [:S-C N:] [:S C-N:]

Since nitrogen is more
electronegative than sulfur, the first
structure should be the major
contributor.

Formal Charges
The actual molecule will be somewhere
in between the first and second
structures.
-1 0

0-

+1

0 - -2

: :

: :

-1

[:S=C=N:] [:S-C N:] [:S C-N:]

The sulfur-carbon bond should be
slightly longer than a double bond, and
the carbon-nitrogen bond should be
slightly shorter than a double bond.

Formal Charges
Some Lewis structures violate the
formal charge guidelines (ex. CO
and BF3).
In either example, if the octet
rule is to be satisfied, a formal
charge of +1 must be placed on the
more electronegative element.

Formal Charges
In the case of BF3, experimental evidence
suggests there is some multiple bonding
between the boron and the fluorine atoms
to create an extended system.

The Valence-Shell
Electron Pair Repulsion
Model

The valence-shell electron pair

repulsion (VSEPR) model predicts the
shapes of molecules and ions by assuming
that the valence shell electron pairs are
arranged as far from one another as
possible.
To predict the relative positions of atoms around a
given atom using the VSEPR model, you first note
the arrangement of the electron pairs around that
central atom.

VSEPR Theory/Molecular
Shapes
Molecules with lone pairs of electrons on
the central atom are described as
distorted from ideal geometry.
NH3 has a bond angle of 106.6o
H2O has a bond angle of 104.5o

Hybrid Orbitals

One might expect the number of

bonds formed by an atom would
equal
its unpaired
electrons.
Chlorine,
for example, generally
forms one
bond and has one unpaired electron.
Oxygen, with two unpaired electrons, usually
forms two bonds.
However, carbon, with only two unpaired
electrons, generally forms four bonds. For
example, methane, CH4, is well known.

Hybrid Orbitals

The bonding in carbon might be

explained as follows:
Four unpaired electrons are formed as an electron
from the 2s orbital is promoted (excited) to the
vacant 2p orbital.
The following slide illustrates this excitation.
More than enough energy is supplied for this
promotion from the formation of two additional
covalent bonds.

Energy

2p

2p

2s

2s

1s

1s

C atom (ground state) C atom (promoted)

Hybrid Orbitals

One bond on carbon would form

using the 2s orbital while the other
three bonds would use the 2p
orbitals.
This does not explain the fact that the four bonds
in CH4 appear to be identical.
Valence bond theory assumes that the four
available atomic orbitals in carbon combine to
make four equivalent hybrid orbitals.

Hybrid Orbitals

Hybrid orbitals are orbitals used to

describe bonding that are obtained
by taking combinations of atomic
orbitals of an isolated atom.
In this case, a set of hybrids are constructed from
one s orbital and three p orbitals, so they are
called sp3 hybrid orbitals.
The four sp3 hybrid orbitals take the shape of a
tetrahedron

Energy

You can represent the

hybridization of carbon in
CH4 as follows.
2p

sp3

sp3
C-H bonds

2s
1s
C atom
(ground state)

1s
C atom
(hybridized state)

1s
C atom
(in CH4)

Hybrid Orbitals

Note that there is a relationship

between the type of hybrid
orbitals and the geometric
arrangement of those orbitals.
Thus, if you know the geometric arrangement,
you know what hybrid orbitals to use in the
bonding description.
Figure 10.24 summarizes the types of
hybridization and their spatial arrangements.

Hybrid Orbitals
Hybrid
Orbitals

Geometric Arrangements

Number
of
Orbitals

Example

sp

Linear

Be in
BeF2

sp2

Trigonal planar

B in BF3

sp3

Tetrahedral

C in CH4

sp3d

Trigonal bipyramidal

P in PCl5

sp3d2

Octahedral

S in SF6

Hybrid Orbitals

To obtain the bonding description of

any atom in a molecule, you proceed
as follows:
1. Write the Lewis electron-dot formula for the
molecule.
2. From the Lewis formula, use the VSEPR
theory to determine the arrangement of
electron pairs around the atom.

Hybrid Orbitals

To obtain the bonding description of

any atom in a molecule, you proceed
as follows:
3. From the geometric arrangement of the
electron pairs, obtain the hybridization type
4. Assign valence electrons to the hybrid orbitals
of this atom one at a time, pairing only when
necessary.

Hybrid Orbitals

To obtain the bonding description of

any atom in a molecule, you proceed
as follows:
5. Form bonds to this atom by overlapping singly
occupied orbitals of other atoms with the
singly occupied hybrid orbitals of this atom.

A Problem to Consider

Describe the bonding in H2O

according to valence bond theory.
Assume that the molecular geometry
is the same as given by the VSEPR
model.
From the Lewis formula for a molecule,
determine its geometry about the central atom
using the VSEPR model.

Copyright Houghton Mifflin

Company.All rights reserved.

Presentation of Lecture
Outlines, 1062

A Problem to Consider

Describe the bonding in H2O

according to valence bond theory.
Assume that the molecular geometry
is the same as given by the VSEPR
model.
The Lewis formula for H O is
2

Copyright Houghton Mifflin

Company.All rights reserved.

Presentation of Lecture
Outlines, 1063

A Problem to Consider

Describe the bonding in H2O

according to valence bond theory.
Assume that the molecular geometry
is the same as given by the VSEPR
model.
From this geometry, determine the hybrid orbitals on
this atom, assigning its valence electrons to these
orbitals one at a time.

A Problem to Consider

Describe the bonding in H2O

according to valence bond theory.
Assume that the molecular geometry
is the same as given by the VSEPR
model.
Note that there are four pairs of electrons about the
oxygen atom.
According to the VSEPR model, these are directed
tetrahedrally, and from the previous table you see that
you should use sp3 hybrid orbitals.

A Problem to Consider

Describe the bonding in H2O

according to valence bond theory.
Assume that the molecular geometry
is the same as given by the VSEPR
model.
Each O-H bond is formed by the overlap of a 1s
orbital of a hydrogen atom with one of the singly
occupied sp3 hybrid orbitals of the oxygen atom.

You can represent the

bonding to the oxygen atom
in H2O as follows:

Energy

2p

sp3

lone
pairs

2s
1s
O atom
(ground state)

sp3

1s
O atom
(hybridized state)

O-H
bonds

1s
O atom
(in H2O)

A Problem to Consider

Describe the bonding in XeF4 using

hybrid orbitals.
From the Lewis formula for a molecule, determine its
geometry about the central atom using the VSEPR
model.

A Problem to Consider

Describe the bonding in XeF4 using

hybrid orbitals.
The Lewis formula of XeF4 is

A Problem to Consider

Describe the bonding in XeF4 using

hybrid orbitals.
From this geometry, determine the hybrid
orbitals on this atom, assigning its valence
electrons to these orbitals one at a time.

A Problem to Consider

Describe the bonding in XeF4 using

hybrid orbitals.
The xenon atom has four single bonds and two
lone pairs. It will require six orbitals to describe
the bonding.
This suggests that you use sp3d2 hybrid orbitals on
xenon.

A Problem to Consider

Describe the bonding in XeF4 using

hybrid orbitals.
Each Xe-F bond is formed by the overlap of a xenon
sp3d2 hybrid orbital with a singly occupied fluorine 2p
orbital.
You can summarize this as follows:

5d

5p

5s
Xe atom (ground state)

5d

sp3d2

Xe atom (hybridized state)

5d

sp3d2
lone pairs

Xe-F bonds

Xe atom (in XeF4)

Multiple Bonding

According to valence bond theory,

one hybrid orbital is needed for
each bond (whether a single or
multiple) and for each lone pair.
For example, consider the molecule ethene.

Multiple Bonding

Each carbon atom is bonded to three

other atoms and no lone pairs, which
indicates the need for three hybrid
orbitals.
This implies sp2 hybridization.
The third 2p orbital is left unhybridized and lies
perpendicular to the plane of the trigonal sp2
hybrids.
The following slide represents the sp2 hybridization
of the carbon atoms.

(unhybridized)

2p

2p

Energy

sp2
2s

1s

1s

C atom (ground state) C atom (hybridized)

Multiple Bonding

To describe the multiple bonding in

ethene, we must first distinguish
between
two
kinds
of
bonds.
A (sigma) bond is a head-to-head overlap of
orbitals with a cylindrical shape about the bond
axis. This occurs when two s orbitals overlap or
p orbitals overlap along their axis.
A (pi) bond is a side-to-side overlap of parallel
p orbitals, creating an electron distribution above
and below the bond axis.

Figure 7

Multiple Bonding

Now imagine that the atoms of

ethene move into position.
Two of the sp2 hybrid orbitals of each carbon
overlap with the 1s orbitals of the hydrogens.
The remaining sp2 hybrid orbital on each carbon
overlap to form a bond.

Multiple Bonding

The remaining unhybridized 2p

orbitals on each of the carbon atoms
overlap side-to-side forming a
bond.

You therefore describe the carbon-carbon

double bond as one bond and one
bond.

Figure 8 Bonding in
Ethylene

Hybridization of Distorted
Molecules
These molecules can be viewed as
having different hybridization in the
bonds and lone pairs.
Since lone pairs are more diffuse and
bulky, they will have greater s
character.
Since bonds are more compact and
directional, they will have greater p
character.

Hybridization of Distorted
Molecules
cos = ss- = p p-1
1

Determine the hybridization of the

bonding and non-bonding orbitals on
nitrogen in ammonia. The bond
angle is 106.6o.

Expanded Coordination
Elements below period 2 can use d
orbitals to make more than 4 bonds.
A trigonal bipyramid, with sp3d
hybridization, is the common structure
for 5 atoms or lone pairs. These
molecules are not fully hybridized. The
trigonal plane is sp2 hybridized, and the
axial positions are a mixture of the pz
and dz2 orbitals.

5 Coordinate Complexes
In molecules with trigonal planar
geometry, not all bond angles and
positions are equivalent.
If the
molecule contains lone pairs of
electrons, they will occupy the
trigonal plane rather than the axial
sites. This will minimize repulsion
within the molecule.

5 Coordinate Complexes
The lone pair of electrons in the
trigonal plane will force the fluorine
atoms closer together.
F
F
101.
187o
S:
F
6o
F

Expanded Coordination
Molecules with 6 atoms or lone pairs
typically take an octahedral shape, with
sp3d2 hybridization. Some complexes with
coordination number 6 may be distorted
prisms.

Expanded Coordination
Molecules with
coordination
number of 7 may
have a pentagonal
bipyramidal shape,
and those with a
coordination
number of 8 may
be a square
antiprism.

Multiple Bonds and

Distortion
Multiple bonds have an influence
on structure similar to that of lone
pairs. The diffuse nature of bonds
causes repulsion with lone pairs and
bonding pairs of electrons.

Electronegativity
Electronegativity is a measure of
an atoms ability to attract electrons
from an atom to which it is bonded.

Mulliken
Electronegativites
Mulliken defined electronegativity as:
(electron affinity + ionization energy)
This approach yields very high
electronegativity values for He and
Ne, even though they do not form
compounds.

Electronegativity Values

Electronegativity and Bond

Angles
Electronegative atoms bonded to a less
electronegative central atom tend to draw
electron density away from the central
atom, thus lowering repulsion.
PF3

PCl3

PBr3

97.8o

100.3o

101o

Hybridization in Period 3
and Below
For central atoms in period 3 or below,
hybridization is less common.
AsH3

PH3

PF3

PCl3

PBr3

91.8o

93.8o

97.8o

100.3o

101o

Steric Number 5
In molecules such as PCl5, the five
bonds are not equal in length.

Steric Number 5
Any lone pairs preferentially
occupy the equatorial positions so as
to minimize electron pair repulsion.

Steric Number 5
In five-coordinate compounds, the
more electronegative (less bulky)
atoms occupy the axial positions.

Steric Number 5
Methyl groups, considered to be less
electronegative than fluorine atoms,
occupy the equatorial sites to minimize
repulsion between the bonding electron
pairs.

Arrangement of
Electron Pairs About
an Atom
2 pairs
Linear

3 pairs
Trigonal planar

5 pairs
Trigonal bipyramidal

4 pairs
Tetrahedral

6 pairs
Octahedral

Copyright Houghton Mifflin

Company.All rights reserved.

Presentation of Lecture
Outlines, 10102

Bond Theory

The geometries of molecules in

terms of their electronic structure.
We will also explore two theories of chemical
bonding: valence bond theory and molecular
orbital theory.
Molecular geometry is the general shape of a
molecule, as determined by the relative positions
of the atomic nuclei.

Dipole Moment
and Molecular
Geometry
The dipole moment is a measure of
the degree of charge separation in a
molecule.
We can view the polarity of individual bonds within
a molecule as vector quantities.
Thus, molecules that are perfectly symmetric have
a zero dipole moment. These molecules are
considered nonpolar.

Dipole Moment and

Molecular Geometry
However, molecules that exhibit any
asymmetry in the arrangement of
electron pairs would have a nonzero
dipole moment.
These molecules
are

considered polar.

Valence Bond Theory

Valence bond theory is an approximate

theory to explain the covalent bond from a
quantum mechanical view.
According to this theory, a bond forms between two
atoms when the following conditions are met.
1. Two atomic orbitals overlap
2. The total number of electrons in both orbitals is
no more than two.

Interpretation of the Formation of

Covalent Bonds in terms of Valence
Bond Theory

(a) NH4+
By Lewis model, the structure is

H
H N H
H

4 single bonds are formed,

one of them is a dative bond.

By VB Theory,
2s
N

2p

1s

3H

1s

H+

Three 2p-1s(half-filled) overlaps

lead to the formation of three N
H single bonds.

N
H

By VB Theory,
2s
N

2p

1s

3H

1s

H+

One 2s(fully-filled)-1s(vacant) overlap leads to

the formation of one N H dative bond.
H
H

N
H

N
H

(b) HCN
By Lewis model, the structure is H-CN

one H-C single bond and

one CN triple bond.

By VB Theory,
2s
C

2p

Only 2 single bonds can be formed.

Promotion of a 2s electron to a 2p
orbital.
2s

C*

2p

C*
2s

N
2s

2p

H
1s

2p

The overlap of one orbital (?) of C* with an 1s

orbital of H gives the C-H single bond.

Overlaps of three orbitals (???) of C* with three

2p orbitals of N give the CN triple bond.

C*
2s

N
2s

2p

H
1s

2p

The 2s electrons on N are non-bonding electrons.

The energy released by forming a stronger

triple bond outweighs the energy required for
promoting an electron from a 2s orbital to a 2p orbital.

(c) SO2

By Lewis model, the three possible

structures are
OS=O,

O=SO,

O=S=O

Most stable

no separation of opposite formal charges.

By VB Theory,
3s

3p

Only two single bonds can be formed.

One 3p electron has to be promoted

to a 3d orbital.

Expansion of Octet.

By VB Theory,
S

3s

3p

octet expansion
3s
S*

3d

3p

3s
S*

2O

3d

3p

2s

2p

Overlaps of two half-filled orbitals (??) of

S* with two half-filled 2p orbitals of an
oxygen atom give a S=O double bond.

A total of two S=O bonds are formed

with two O atoms

3s
S*

2O

3d

3p

2s

2p

O
Non-bonding electrons :
S* 3s2 ;
O 2s2 and 2p2

3s

3p

octet expansion
3s
S*

3d

3p

The energy released by forming of two

stronger double bonds outweighs the energy
required for promoting an electron from a 3p
orbital to a 3d orbital.

Molecular Orbital Theory

Molecular orbital theory is a

theory of the electronic structure of
molecules in terms of molecular
orbitals, which may spread over
several atoms or the entire
As atoms approach each other and their atomic
molecule.
orbitals overlap, molecular orbitals are formed.

In the quantum mechanical view, both a bonding

and an antibonding molecular orbital are formed.

Molecular Orbital Theory

For example, when two hydrogen atoms

bond, a 1s (bonding) molecular orbital
is formed as well as a 1s * (antibonding)
molecular orbital.
The following slide illustrates the relative energies of
the molecular orbitals compared to the original
atomic orbitals.
Because the energy of the two electrons is lower
than the energy of the individual atoms, the molecule
is stable.

H atom

H2 molecule

H atom

1s*
1s

1s

1s

Bond Order

The term bond order refers to the

number of bonds that exist between
two
Theatoms.
bond order of a diatomic molecule is
defined as one-half the difference between
the number of electrons in bonding orbitals,
nb, and the number of electrons in
antibonding orbitals, na.

bond order

1
2

(n b - n a )

Electronic
Configurations of
Diatomic Molecules

In heteronuclear diatomic
molecules, such as CO or NO, we
must have additional molecular
orbitals.
The overlap of p orbitals results in two
sets of orbitals (two bonding and two
antibonding) and one set of orbitals
(one bonding and one antibonding).
The next slide illustrates the relative
energies of these molecular orbitals.

The arrows show the

occupation of molecular
orbitals by the valence
electrons in N2.

N
N

The molecular
electron
configuration for
2 * 2 be:4
N2 would

2s

2s

2p

2p

2
Bond
order =
(8-2)/2 = 3

Lets Practice!
What is the molecular configuration
of an O2 molecule?
How many total valence electrons in
the molecule? 12
Using Fig. 12 fill in the molecular
orbitals from the bottom up with the 12
total valence electrons.
2s2*2s22p42p2*2p2
4)/2=2

Bond order = (8- O=O

Lets Practice!
What is the molecular configuration
of an F2 molecule?
How many total valence electrons in
the molecule?
14
Using Fig. 13 fill in the molecular
orbitals from the bottom up with the 14
total valence electrons.
2s2*2s22p42p2*2p4
6)/2=1

Bond order = (8- F-F

Copyright Houghton Mifflin

Company.All rights reserved.

Presentation of Lecture
Outlines, 10129

Figure 9 Bonding in HCl.

Figure 10. Spatial arrangement of sp3 hybrid

orbitals.

Figure 11 Diagrams of hybrid orbitals showing their spatial

arrangements.

Figure 12 Relative Energies of Molecular

Orbitals of Homonuclear Diatomic
Molecules (Excluding K Shells)

O2

Figure 13 Relative Energies of Molecular

Orbitals of Homonuclear Diatomic
Molecules (Excluding K Shells)

F2