CHM012

Chemistry for
Engineers

Molecular Structure
and Orbitals
BILLACURA, M.D.
 Molecular Structure

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
By Gillespie and Nyholm, 1957

“…that the electrostatic repulsion is reduced to a

minimum when various regions of electron density
position are as far as possible.”
Regions of electron density:
a. Covalent bonds (bonding pairs)
b. Unshared pair of electrons (lone pairs)

The structure around a given atom is determined principally

by minimizing electron pair repulsions

BILLACURA, M.D.
 Bonding Pairs and Lone Pairs
Bonding pairs are shared between two nuclei
• Electrons can be close to either nucleus
• They are relatively confined between the
two nuclei

Lone pairs center around just one nucleus, and

both electrons choose that nucleus
Lone pairs need more space than bonding pairs
• They compress the angles between bonding
pairs

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
1. Rules on repulsion

bond pair – bond pair

<
Lone pair – bond pair
<
Lone pair – Lone pair
❖ The bond angle between bonding pairs
decreases as the number of lone pairs
increases on the central atom

CH4 NH3 H2O

Note: decreasing electron pair repulsion Number of Lone Pairs 0 1 2
increases bond angle Bond Angle 109.5° 107° 104.5°

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
2. Effect of electronegativity
- Increasing size and lower electronegativity of the central atom permit the lone pairs to
be drawn out further, thus decreasing the repulsion between bonding pairs.

H2O H2S H2Se

104.5o 92.1o 90.6o

strongest weakest
bp-bp repulsion bp-bp repulsion

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
3. Repulsion exerted by bonding pairs decreases as the electronegativity of the bonded atoms increases.

H2O F2O

104.5o 103.2o

decreasing bp-bp repulsion

BILLACURA, M.D.
 Example
Arrange the following molecules in the increasing
order of bond angle:

H2O, CH4, SF6, BF3, NH3 , BeF2

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
4. Repulsion exerted by triple bonds are greater than those in single bonds.
❖ While using the VSEPR model, a double bond must be considered as one effective pair
The two pairs involved in the double bond are not independent pairs
The double bond acts as one center of electron density that repels other electron pairs
❖ With molecules that exhibit resonance, any one of the resonance structures can be used to predict its
molecular structure using the VSEPR model

180o 120o 109o

decreasing bond angle due to decreasing repulsion

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
5. In trigonal bipyramidal
❖ When there are five electron pairs, the structure that produces minimal repulsion is a trigonal
bipyramid. It consists of two trigonal-based pyramids that share a common base

a. Lone pair occupy the equatorial position (120o away)

b. Double bonds occupy equatorial positions
c. Less electronegative atoms occupy equatorial positions

axial
F F

Cl
S F P Cl
F Cl

F F
equitorial
SF4 PF2Cl3
seesaw Trigonal bypyramid

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
6. In octahedral
❖ The best arrangement for six pairs of electrons around a given atom is the octahedral structure. This
structure has 90-degree bond angles

a. A lone pair occupy in any position

b. 2 lone pairs, the 2nd lone pair must be in opposite position of the 1st lone pair (180o)

F F
F F
Br Xe
F
F F
F

XeF4
BrF5

BILLACURA, M.D.
 Valence Shell Electron-Pair Repulsion (VSEPR)
7. Multiple bonds do not affect the gross stereochemistry. The geometry is primarily
determined by:
a. Lone pairs
b. Bonding pairs

The presence of multiple bond will only affect, bond angle and bond distance.

BILLACURA, M.D.
 Molecules Containing No Single Central Atom
The VSEPR model can accurately determine the structure of complicated
molecules such as methanol. The Lewis structure is:
There are four pairs of electrons around the C and O atoms, which give rise to
a tetrahedral arrangement
Space requirements of the lone pairs distort the arrangement

(a) The arrangement of

electron pairs and
atoms around the
carbon
(b) The arrangement of
bonding and lone
pairs around oxygen
(c) The molecular
structure

BILLACURA, M.D.
 Accuracy of the VSEPR Model

It aptly predicts the molecular structures of most molecules formed from

non-metallic elements
It can be used to predict the structures of molecules with hundreds of
atoms
It fails to determine the molecular structure in certain instances
• Phosphine (PH3) and ammonia (NH3) have similar Lewis structures but
different bond angles—94 degrees and 107 degrees, respectively

BILLACURA, M.D.
 Example
• Determine the shape and bond angles for each of the
following molecules:
a) HCN

b) PH3

c) SF4

d) O3

e) KrF4

BILLACURA, M.D.
 Example
When phosphorus reacts with excess chlorine gas, the
compound phosphorus pentachloride (PCl5) is formed. In
the gaseous and liquid states, this substance consists of PCl5
molecules, but in the solid state it consists of a 1:1 mixture
of PCl4+ and PCl6 − ions. Predict the geometric structures of
PCl5, PCl4+ , and PCl6− .

BILLACURA, M.D.
Dipole Moment
A molecule that has a center of positive charge and a center of negative charge is said to be
dipolar or to possess a dipole moment.
It is represented by an arrow pointing to the negative charge center. The tail indicates the
positive charge center.
Electrostatic potential diagrams can also be used to represent dipole moment.
The colors of visible light are used to show variation in distribution of charge.
• Red - Most electron-rich region
• Blue - Most electron-poor region

BILLACURA, M.D.
Bond Polarity
Any diatomic molecule with polar bonds will exhibit dipole moments
This behaviour can also be exhibited by polyatomic molecules
Few molecules possess polar bonds but lack dipole moment
• Occurs when the individual bond polarities are arranged in a manner that they cancel each other out

BILLACURA, M.D.
Comparison of the Polarity of Two Molecules
ü A POLAR
molecule

ü A
NONPOLAR
molecule

BILLACURA, M.D.
 Example
Predict the molecular structure of the
sulfur dioxide molecule. Is this
molecule expected to have a dipole
moment?

BILLACURA, M.D.
 Example
For each of the following molecules, show the direction of the
bond polarities and indicate which ones have a dipole moment:
a) HCl

b) Cl2

c) SO3 (planar molecule with the oxygen atoms spaced evenly

around the central sulfur atom)

d) CH4 (tetrahedral with the carbon atom at the center)

e) H2S (V-shaped with the sulphur atom at the point)

BILLACURA, M.D.
 Valence Bond Theory
In Valence-Bond Theory, electrons of two atoms begin to occupy the
same space.
This is called “overlap” of orbitals.
The sharing of space between two electrons of opposite spin results
in a covalent bond.

Increased overlap brings the

electrons and nuclei closer
together until a balance is
reached between the like
charge repulsions and the
electron-nucleus attraction.
Atoms can’t get too close
because the internuclear
repulsions get too great.

BILLACURA, M.D.
Hybrid Orbitals
Hybrid orbitals form by “mixing” of atomic orbitals to create
new orbitals of equal energy, called degenerate orbitals.

When two orbitals “mix” they create two orbitals; when

three orbitals mix, they create three orbitals; etc.

BILLACURA, M.D.
 sp hybrid orbital
When we look at the orbital diagram for beryllium (Be), we see that
there are only paired electrons in full sublevels.
Beryllium makes electron deficient compounds with two bonds for Be.
Why? sp hybridization (mixing of one s orbital and one p orbital)

Mixing the s and p orbitals yields two degenerate orbitals that are
hybrids of the two orbitals.
– These sp hybrid orbitals have two lobes like a p orbital.
– One of the lobes is larger and more rounded, as is the s orbital.

BILLACURA, M.D.
sp hybrid orbital
These two degenerate orbitals would align
themselves 180° from each other.
This is consistent with the observed geometry of Be
compounds (like BeF2) and VSEPR: linear.

BILLACURA, M.D.
 sp 2 hybrid orbital
Using a similar model for boron leads to three
degenerate sp2 orbitals.
Gives a trigonal planar arrangement of atomic
orbitals with bond angles of 120 degrees
It occurs on the combination of one 2s and two 2p
orbitals
One p orbital is not used it is oriented perpendicular
to the plane of the sp2 orbitals

1s sp2 2p

BILLACURA, M.D.
 sp 3 hybrid orbital
With carbon, we get four degenerate sp3 orbitals.
It can be observed upon combination of one 2s and three 2p
orbitals
Whenever an atom requires a set of equivalent tetrahedral
atomic orbitals, this model assumes that the atom adopts a
set of sp3 orbitals. The atom becomes sp3 hybridized

1s sp3

BILLACURA, M.D.
What Happens with Water?
❖ In H2O molecule, the angle question: Why is it
104.5° instead of 90°?
❖ Oxygen has two bonds and two lone pairs—
four electron domains.
❖ The result is sp3 hybridization!

BILLACURA, M.D.
Types of Bond - How does a double or triple bond form?
Two types of bonds:
Sigma (σ) bonds – are characterized by:
– head-to-head overlap.
– cylindrical symmetry of electron density about the internuclear
axis.
Pi (π) bond – are characterized by:
– side-to-side overlap.
– electron density above and below the
internuclear axis.

BILLACURA, M.D.
 Double and Triple Bonds
Single bonds are always
σ-bonds.
Multiple bonds have one
σ-bond, all other bonds
are π-bonds.

Triple Bond
Double Bond

BILLACURA, M.D.
Bonding orbitals in CO2

BILLACURA, M.D.
 Example
a. Draw the Lewis structure for HCN
b. Which of the hybrid orbitals are used?

c. Draw HCN and:

• Show all the bonds between the atoms

• Label each σ or π bond

BILLACURA, M.D.
 Hybrid Orbitals – Hypervalent Molecules

ü The elements which have more than an octet

ü Valence-Bond model would use d orbitals to make more
than four bonds.
ü This view works for period 3 and below.
ü Theoretical studies suggest that the energy needed would
be too great for this.

BILLACURA, M.D.
 dsp3 Hybridization
ü It is a combination of one d, one
s, and three p orbitals
ü It results in a trigonal
bipyramidal arrangement of five
equivalent hybrid orbitals
ü The image illustrates hybrid
orbitals in a phosphorus atom

BILLACURA, M.D.
 d sp
2 3 Hybridization
ü An atom is d2sp3 hybridized
when there is a combination
of two d, one s, and three p
orbitals
ü It results in an octahedral
arrangement of six equivalent
hybrid orbitals
ü The image illustrates the
orbitals in a sulfur atom
BILLACURA, M.D.
 Example
How is the xenon atom in XeFe4 hybridized?

Solution
XeFe4 has six pairs of electrons around xenon that are arranged octahedrally to minimize repulsions. An octahedral
set of six atomic orbitals is required to hold these electrons, and the xenon atom is d2sp3 hybridized

BILLACURA, M.D.
Hybrid Orbitals - Summary

BILLACURA, M.D.
 Example
For each of the following molecules or ions, predict the
hybridization of each atom, and describe the molecular
structure.
a. CO

b. BF4
−

c. XeF2

BILLACURA, M.D.
 Molecular Orbital Theory
ü Wave properties are used to describe the energy of the electrons in a molecule.

ü Molecular orbitals have many characteristics like atomic orbitals:

– maximum of two electrons per orbital
– Electrons in the same orbital have opposite spin.
– Definite energy of orbital
– Can visualize electron density by a contour diagram

ü They differ from atomic orbitals because they represent the entire molecule, not a single atom.
Whenever two atomic orbitals overlap, two molecular orbitals are formed: one bonding, one
antibonding.

Ø Bonding orbitals are constructive combinations of atomic orbitals.

Ø Antibonding orbitals are destructive combinations of atomic orbitals. They have a new feature
unseen before: A nodal plane occurs where electron density equals zero.
BILLACURA, M.D.
 Molecular Orbital Theory
Ø Whenever there is direct overlap of
orbitals, forming a bonding and an
antibonding orbital, they are called
sigma (σ) molecular orbitals. The
antibonding orbital is distinguished
with an asterisk as σ*. Here is an
example for the formation of a
hydrogen molecule from two atoms.

Note: The number of orbitals are

conserved. The number of MOs will
always be equal to the number of atomic
orbitals used to construct them.

BILLACURA, M.D.
Molecular Orbital Diagram
• An energy-level diagram, or MO diagram
shows how orbitals from atoms combine to give
the molecule.
• In H2 the two electrons go into the bonding
molecular orbital (lower in energy).
• Bond order - It refers to the difference between
the number of bonding electrons and the
number of antibonding electrons divided by 2.
Larger bond order is generally related to greater bond
strength

BILLACURA, M.D.
 Can H2- and He2 form?
Hydrogen ion, H2- Helium molecule, He2

BILLACURA, M.D.
 Homonuclear Diatomic Molecules
These molecules are composed of two identical atoms
The valence orbitals significantly contribute to the MO of a
particular molecule.
Electron probability in such molecules is high above and below the
line between the nuclei.

❖ Both orbitals are pi (π) molecular orbitals

Bonding MO - π2p
Antibonding MO - π2p*

For atoms with both s and p orbitals, there are two types of
interactions:
The s and the p orbitals that face each other overlap in σ
fashion.
The other two sets of p orbitals overlap in π fashion – These
are, again, direct and “side-ways” overlap of orbitals.

BILLACURA, M.D.
 Homonuclear Diatomic Molecules
The resulting MO diagram:
– There are σ and σ* orbitals from s and
p atomic orbitals.
– There are π and π* orbitals from p
atomic orbitals.
– Since direct overlap is stronger, the
effect of raising and lowering energy is
greater for σ and σ*.

BILLACURA, M.D.
 s and p Orbital Interactions

ü In some cases, s orbitals can interact wit the pz orbitals more than the px and py orbitals.
ü It raises the energy of the pz orbital and lowers the energy of the s orbital.
ü The px and py orbitals are degenerate orbitals.
BILLACURA, M.D.
 MO Diagram and Magnetism
Diamagnetism is the result of all electrons in every orbital being
spin paired. These substances are weakly repelled by a magnetic
field. Causes a substance to be repelled from the inducing magnetic
field

Paramagnetism is the result of the presence of one or more

unpaired electrons in an orbital. Causes a substance to be attracted
into the inducing magnetic field
Example: Is oxygen (O2) paramagnetic or diamagnetic? Look back at
the MO diagram! It is paramagnetic.

BILLACURA, M.D.
MO Diagram of Homonuclear Diatomic
Molecules

BILLACURA, M.D.
 Example
Use the molecular orbital model to predict the bond
order and magnetism of each of the following
molecules:

a) Ne2
b) P2

BILLACURA, M.D.
Heteronuclear Diatomic Molecules
Ø Diatomic molecules can consist of atoms from different elements.
Ø The atomic orbitals have different energy, so the interactions change slightly.
Ø The more electronegative atom has orbitals lower in energy, so the bonding orbitals will more
resemble them in energy.
Example: HF
molecule
Consider the HF molecule and assume that
fluorine uses only its 2p orbitals to bond to
hydrogen
The MOs for HF are composed of fluorine 2p
and hydrogen 1s orbitals
The fluorine 2p orbital is lower in energy than
the hydrogen 1s orbital
The σ MO holding the binding electron pairs Electron probability
will show higher electron probability closer to distribution
fluorine
Electron pairs are not equally shared Partial MO energy-level
diagram
BILLACURA, M.D.
 Example
Use the molecular orbital model to predict the magnetism and bond order of the NO, NO+
and CN− ions

BILLACURA, M.D.