Chem 16 General Chemistry 1

05 Molecular Geometry and Bonding Theories

Dr. Gil C. Claudio

Second Semester 2014-2015
Table of Contents

Contents
1 Valence-Shell Electron-Pair Repulsion Theory

2 Molecular Shape and Molecular Polarity

3 Valence Bond Theory

3.1 Valence Bond Theory . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Hybrid Orbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Multiple Covalent Bonds . . . . . . . . . . . . . . . . . . . . . . .

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8
8
10

4 Molecular Orbital Theory

4.1 Molecular Orbitals . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 MO Energy Level Diagrams . . . . . . . . . . . . . . . . . . . . .

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10
13

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffrey D. Madura, and Carey Bisonnette.

1 Valence-Shell Electron-Pair Repulsion Theory

VSEPR Theory
The valence-shell electron-pair repulsion (VSEPR) theory is a theory used
to predict probable shapes of molecules and polyatomic ions based on the
mutual repulsions of electron pairs found in the valence shell of the central
atom in the structure.
Electron pairs repel each other, whether they are in chemical bonds (bond
pairs) or unshared (lone pairs). Electron pairs assume orientations about
an atom to minimize repulsions.
Molecular Geometry
Electron-group geometry refers to the geometrical distribution about a
central atom of the electron pairs in its valence shell.
Molecular geometry refers to the geometric shape of a molecule or polyatomic
ion. In a species in which all electron pairs are bond pairs, the molecular
geometry is the same as the electron-group geometry. In other cases, the two
properties are related but not the same.

Repulsion Between Electron Pairs

Lone-pair electrons spread out more than do bond-pair electrons. Thus the
amount of repulsion between bonding pairs (BP) and lone pairs (LP) is related
by
LP-LP > LP-BP > BP-BP
2 Electron Pairs: Linear

en.wikipedia.org/wiki/VSEPR theory

linear
BeCl2 , CO2
3 Electron Pairs: Trigonal Planar

en.wikipedia.org/wiki/VSEPR theory

trigonal planar
BF3 , CO32 , NO3 , SO3
bent
NO2 , SO2 , O3
4 Electron Pairs: Tetrahedral

en.wikipedia.org/wiki/VSEPR theory

tetrahedral
CH4 , PO43 , SO42 , ClO4
trigonal pyramidal
NH3 , PCl3
bent
H2 O, OF2
5 Electron Pairs: Trigonal Bipyramidal

en.wikipedia.org/wiki/VSEPR theory

trigonal bipyramidal
PCl5
see-saw
SF4
t-shaped
ClF3 , BrF3
linear
XeF2 , I3
6 Electron Pairs: Octahedral

en.wikipedia.org/wiki/VSEPR theory

octahedral
SF6
square-pyramidal
ClF5 , BrF5
square-planar
XeF4
Applying VSEPR Theory
The following strategy can be used for predicting the shapes of molecules.
1. Draw a plausible Lewis structure of the molecule or polyatomic ion.
2. Determine the number of electron groups around the central atom, and
identify them as being either bond-pair electron groups or lone pairs of
electrons.
3. Establish the electron-group geometry around the central atom linear,
trigonal planar, tetrahedral, trigonal bipyramidal, or octahedral.
4. Determine the molecular geometry from the positions of the atoms
bonded directly to the central atom.
Examples
Determine the molecular shape and the ideal bond angles of
1. PF3
2. COCl2
3. ICl4
4. SbF5
5. BrF5
5

ANSWERS
1. trigonal pyramidal, ideal angle is 109.5
2. trigonal planar, ideal angle is 120
3. square planar
4. trigonal bipyramidal, ideal angles are 120 and 90
5. square pyramidal, bond angles are smaller than the ideal 90
Bigger Molecules
VSEPR theory can also be applied to molecules or polyatomic anions with
more than one central atom. In such cases, the geometric distribution of
terminal atoms around each central atom must be determined and the results
then combined into a single description of the molecular shape.
Bigger Molecules: Ethanol
Ethanol, CH3 CH2 OH

en.wikipedia.org/wiki/File:Ethanol-3D-balls.png

Bigger Molecules: Cyclohexane

Cyclohexane, C6 H12
H2C

CH2
CH2

H2C

CH2

H2C

commons.wikimedia.org/wiki/ File:Cyclohexane-compressed.svg

en.wikipedia.org/wiki/File: Cyclohexane-chair-2D-stero-skeletal.png

en.wikipedia.org/wiki/File: Cyclohexane-chair-3D-balls.png

2 Molecular Shape and Molecular Polarity

Polar Molecules in an Electric Field (1)
In an electrical condenser (or capacitor)
polar molecules orient randomly when the field is off.
when the electric field is turned on, the polar molecules orient in the field
between the charged plates so that the negative ends of the molecules are
toward the positive plate and vice versa.
Dipole Moment
Dipole moment is a measure of the extent to which a separation exists
between the centers of positive and negative charge within a molecule.
= d where is the partial charge and d is the distance.
The unit used to measure dipole moment is the debye, 3.34 1030 C m.
Partial Charges in HCl
The partial charges in the HCl molecule can be computed as
=

1.03 D 3.34 1030 Cm/D

=
= 2.70 1020 C
d
127.4 1012 m

This charge is about 17% of the charge on an electron (1.602 1019 C) and
suggests that HCl is about 17% ionic.
Polar Water Molecule

O
H

en.wikipedia.org/wiki/ File:Water-elpot-transparent-3D-balls.png

HF and NH3 Polarity

commons.wikimedia.org/wiki/ File:Dipoli acido fluoridrico.png

commons.wikimedia.org/wiki/ File:Dipoli ammoniaca.png

Exercise
Determine the polarity of the molecules:
Cl2 , ICl, BF3 , NH3 , NO, SO2
ANSWERS:
polar: ICl, NH3 , NO, SO2
nonpolar: Cl2 and BF3

3 Valence Bond Theory

3.1

Valence Bond Theory

Other Bonding Theories

All scientific models have limitations because they are simplifications of
reality.
The strength of the Lewis theory is in the ease with which it can be
applied.
The molecular shapes proposed by VSEPR theory are generally in good
agreement with experimental results.
However, neither method yields quantitative information about bond
energies and bond lengths. Also, Lewis theory has problems with
odd-electron species and resonance structures.
Using other theories help give a better picture of the nature of a chemical bond.
Valence Bond Theory
The valence bond method treats a covalent bond in terms of the overlap
of pure or hybridized atomic orbitals. Electron probability (or electron charge
density) is concentrated in the region of overlap.
Overlap is actually an interpenetration of two orbitals.
The valence-bond method gives a localized electron model of bonding:
Core electrons and lone-pair valence electrons retain the same orbital
locations as in the separated atoms, and the charge density of the bonding
electrons is concentrated in the region of orbital overlap.

Central Themes of VB Theory

From the main principle of VB theory are derived three central ideas:
1. The region of space formed by the overlapping orbitals has a maximum
capacity of two electrons that must have opposing spins.
2. The bond strength depends on the attraction of the nuclei for the shared
electrons. The greater the orbital overlap, the stronger the bond.
3. The valence atomic orbitals in the molecule are different from those in
the isolated atoms. Mathematical mixing of specific combinations of
nonequivalent orbitals gives rise to new atomic orbitals that would lead
to the most stable bonds. This is called hybridization.

3.2

Hybrid Orbitals

Hybridization
Hybridization refers to combining pure atomic orbitals to generate hybrid
orbitals in the valence bond approach to covalent bonding.
A hybrid orbital is one of a set of identical orbitals reformulated from
pure atomic orbitals and used to describe certain covalent bonds.
Hybridization occurs only when bonds are being formed.
In a hybridization scheme, the number of hybrid orbitals equals the total
number of atomic orbitals that are combined.
Energy Stabilization
Ground State

Excit
ed state

2p

2p

2s

2s

Hybridisation

sp3
1 unhybridised
p orbital

2p

sp2
2s

2 unhybridised
p orbitals

2p

sp
2s
commons.wikimedia.org/wiki/File:Hybridisation.svg

Summary of sp x Orbitals

109.5

commons.wikimedia.org/wiki/ File:AE4h.svg

120

A
commons.wikimedia.org/wiki/ File:AE3h.svg

180

A
commons.wikimedia.org/wiki/ File:AE2h.svg

Hybrid Orbitals and VSEPR (1)

We can choose the likely hybridization scheme for a central atom in a
structure in the valence-bond method by
writing a plausible Lewis structure for the species of interest
using VSEPR theory to predict the probable electron-group geometry of
the central atom
selecting the hybridization scheme corresponding to the electron-group
geometry
Hybrid Orbitals and VSEPR (2)
Some hybrid orbitals and their geometric orientations
hybrid
orbitals
sp
sp2
sp3
sp3 d
sp3 d2

geometric
orientation
linear
trigonal-planar
tetrahedral
trigonal-bipyramidal
octahedral

example
BeCl2
BF3
CH4
PCl5
SF6

Proposing Hybridization and Shape

PHMB 10e, Example 11-2
Predict the shape of the XeF4 molecule and a hybridization scheme
consistent with this prediction.
ANSWER: square-planar, sp2 d2

3.3

Multiple Covalent Bonds

Bond and Bond

A sigma bond () results from the end-to-end overlap of simple or
hybridized atomic orbitals along the straight line joining the nuclei of the
bonded atoms.
A pi bond ( bond) results from the side-to-side overlap of p orbitals,
producing a high electron charge density above and below the line joining the
bonded atoms.

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Bonding Scheme in Formic Acid

Formic acid, HCOOH, is an irritating substance released by ants when they
bite (formica is Latin, meaning ant). The Lewis structure, hybridization and
bonding schemes are shown below.

4 Molecular Orbital Theory

Lewis, VSEPR, and VB
Lewis structures, VSEPR theory, and the valence-bond method make a
potent combination for describing covalent bonding and molecular structures.
However, none of these methods provides an explanation of the
electronic spectra of molecules, why oxygen is paramagnetic, or why H2+
is a stable species.
Another theory is needed.

4.1

Molecular Orbitals

Molecular Orbital Theory

Molecular orbital theory describes the covalent bonds in a molecule
by replacing atomic orbitals of the component atoms by molecular orbitals
belonging to the molecule as a whole.
A set of rules is used to assign electrons to these molecular orbitals,
thereby yielding the electronic structure of the molecule.
Like atomic orbitals, molecular orbitals are mathematical functions, but
we can relate them to the probability of finding electrons in certain
regions of a molecule.
Like an atomic orbital, a molecular orbital can accommodate just two
electrons, and the electrons must have opposing spins.
Bonding and Antibonding Orbitals (1)
Wave functions can combine via constructive interference (addition) which
leads to a bonding orbital.
A bonding molecular orbital describes regions of high electron
probability or charge density in the internuclear region between two
bonded atoms.
Wave functions can also combine via destructive interference (subtraction)
which leads to an antibonding orbital.
An antibonding molecular orbital describes regions in a molecule in
which there is a low electron probability or charge density between two
bonded atoms.
Bonding and Antibonding Orbitals (2)

commons.wikimedia.org/wiki/ File:Wave functions anti-binding.svg

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commons.wikimedia.org/wiki/ File:Dihydrogen-LUMO-phase-3D-balls.png

commons.wikimedia.org/wiki/ File:Wave functions binding.svg

commons.wikimedia.org/wiki/ File:Dihydrogen-HOMO-phase-3D-balls.png

H2 MO Diagram

E
1 u*

H1s

H1s
1 g

Basic Ideas Concerning MOs

Some ideas on molecular orbitals and assigning electrons to them
1. The number of molecular orbitals (MOs) formed is equal to the number
of atomic orbitals combined.
2. Of the two MOs formed when two atomic orbitals are combined, one is
a bonding MO at a lower energy than the original atomic orbitals. The
other is an antibonding MO at a higher energy.
3. In ground-state configurations, electrons enter the lowest energy MOs
available.
4. The maximum number of electrons in a given MO is two.
5. In ground-state configurations, electrons enter MOs of identical energies
singly before they pair up.

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Bond Order
Bond order is one-half the difference between the numbers of electrons in
bonding and in antibonding molecular orbitals in a covalent bond.
bond order = 12 (# e in bonding MO - # e in antibonding MO)
Bond: s + p

commons.wikimedia.org/wiki/File:OrbitalSigma-pp.png

Bond

commons.wikimedia.org/wiki/File:OrbitalPiAnty-pp.png

commons.wikimedia.org/wiki/File:OrbitalPi.png

4.2

MO Energy Level Diagrams

He2 MO Diagram

E
1 u*

1s

1s

1 g
He

He-He

13

He

Period 2 Diatomic MO Diagrams

*
*
2p

2p

2s

2s

*
1s

1s

Homonuclear Diatomic MO Diagrams (1)

The following features are notable
The 2s AOs are substantially lower in energy than the 2p AOs. Thus
both orbitals formed from the 2s orbitals are lower in energy than the
lowest-energy MO derived from the 2p AOs.
The overlap of two 2pz orbitals is greater than the two 2p x or 2py orbitals.
MO
Thus the 2p MO is lower than the 2p MOs, and the antibonding 2p

is higher in energy than the 2p MOs.

MOs are doubly degenerate.
Both 2p and 2p

Homonuclear Diatomic MO Diagrams (2)

A further modification is necessary
B2 , C2 , N2 : Due to the small energy difference between the 2s and the 2p
orbitals, there is a strong 2s-2p interaction. The modified 2s (with some
2p mixed in) goes down in energy, and the modified 2p (with some 2s
mixed in) goes up in energy producing a different ordering of energy
levels.
O2 , F2 , Ne2 : The situation is as expected due to the large energy
difference between the 2s and the 2p orbitals which leads to a weak 2s-2p
interaction.
B2 Ne2 MO Diagrams

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Large 2s-2p interaction

B2

C2

Small 2s-2p interaction

N2

O2

F2

Ne 2

*2p

*2p

*2p

*2p

2p

2p

2p

2p

*2s

*2s

2s

2s

Heteronuclear Diatomic
If the atoms in the heteronuclear diatomic molecules do not differ too
greatly in electronegativities, their MOs resemble those in homonuclear
diatomics.
The energy of the AOs of the more electronegative atom is lower than
those of the less electronegative atom.
An MO in a heteronuclear diatomic molecule has a greater contribution
from the AO to which it is closer in energy.
HF MO Diagram

commons.wikimedia.org/wiki/File:Diagramme HF.jpg

CO MO Diagram

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commons.wikimedia.org/wiki/File:MO COeng.svg

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