Chapter 10: Chemical Bonding

and Molecular Structure

• Molecules containing three or more atoms
may have many different shapes
• Almost all are “three-dimensional”
• All these shapes are made from five
geometrical structures
• The shapes may be classified according to
the number of electron domains they
contain around the central atom
• A simple and useful model of electron
domains is the valence shell electron shell
repulsion model or VSEPR model
• There are two types of electron domains
– Bonding domains involve electron pairs that
are involved in bonds between two atoms
– Nonbonding domains contain electron pairs
that are associated with a single atom
• All electrons in a single, double, or triple
bond are considered to be in the same
bonding domain
• A nonbonding domain contains a lone pair
(unshared pair of electrons) or an unpaired
electron for a molecule with an odd number
of valence electrons
• The VSEPR model is based on the notion
that electron domains keep as far away as
possible from one another
• The shapes expected for different numbers
of electron domains around a central atom
may be summarized:
• The number of sets of electron domains
must be know to predict the shape of a
molecule or ion
• This can be done using any correctly draw
Lewis structure
• The molecular shape describes the
arrangement of the atoms, not the
arrangement of the domains
• Consider the case of four domains
 For a given
number of
domains, the
molecular
shape
changes as
the number of
bonding
domains
decreases.

• Five and six domains have more

possibilities
Molecular shapes
with five domains
around the central
atom. Four different
molecular structures
are possible,
depending on the
number of
nonbonding domains
around the central
atom M.
Molecular shapes
with six domains
around the central
atom. Only three
different molecular
shapes are observed,
depending on the
number of
nonbonding domains
around the central
atom M.
• Polar molecules attract each other

Polar molecules tend to

orient themselves so
that the positive end of
one molecular dipole is
near the negative end of
another.

• The dipole moment can be determined

experimentally
• It turns out that many molecules with polar
bonds are nonpolar
• This is possible because certain
arrangements of bond dipoles cancel
• The polarity of a molecule can be predicted
by taking the vector sum of the bond
dipoles
• Bond dipoles are usually shown as crossed
arrows, where the arrowhead indicates the
negative end
• Symmetric molecules such as these are
nonpolar because the bond dipoles cancel
• All of the basic shapes are symmetric, or
balanced, if all the domains and groups
attached to them are identical
 Chloroform, CCl3H, is
asymmetric. The vector
sum of the bond dipoles
is nonzero giving the
molecule a net dipole.

• A molecule will be nonpolar if: (a) the

bonds are nonpolar, or (b) there are no
lone pairs in the valence shell of the
central atom and all the atoms attached to
the central atom are the same
 Nonbonding domains
occur for both water and
ammonia: the bond
dipoles do not cancel,
and the molecules are
polar
• Lewis structures and VSEPR do not tell us
why electrons group into domains as they do
• How atoms form covalent bonds in
molecules requires an understanding of how
orbitals interact
• Valence bond (VB) theory and molecular
orbital (MO) theory are two important
theories of covalent bonding
• According to VB theory, a bond between
two atoms is formed when a pair of
electrons with their spins paired is shared
by two overlapping atomic orbitals, one
orbital from each of the atoms joined by the
bond
 The VB view of the formation of the covalent bond in H2

• The amount the potential energy is lowered

when the bond forms depends, in part, on
the extent of orbital overlap
• Therefore, atoms tend to position
themselves so the the maximum amount of
orbital overlap occurs
• This yields the minimum potential energy
and the strongest bonds
• The fluorine atom has a singly occupied 2p
orbital
• It can overlap with the hydrogen 1s orbital
to form the single bond in hydrogen fluoride
 The VB view of the formation of the bond in HF. Only
the half-filled fluorine 2p orbital is shown.

• More complicated overlap is common

• In hydrogen sulfide (H2S) two half-filled 3p
orbitals on sulfur overlap with the 1s
orbitals on two hydrogen atoms
 The H 1s orbitals
position themselves
for maximum
overlap with the S
3p orbitals. The
predicted 90º bond
angle is very close
to the experimental
value of 92º.

• There are many molecules with shapes and

bond angles that fail to fit the VB model as
developed
• The VSEPR model correctly predicts many
of these shapes and angles
• A realistic description of bonds often
requires combining or blending two or more
atomic orbitals
• The blended orbitals that result are called
hybrid atomic orbitals
• The new orbitals have different shape and
directional properties
Mixing the 2s
and (one) 2p
atomic orbital
results in a pair
of sp hybrid
orbitals. Note
that the large
lobes of these
hybrid orbitals
point in
opposite
directions.
VB view of bonding
in BeH2. The two H
1s orbitals approach
the large lobes of the
two sp hybrid orbitals
on Be (a). Overlap (b)
and a representation
of the electron
distribution after the
two Be-H bonds have
formed (c). (The
correct experimental
geometry is
predicted.)
• When an s orbital combines with two p
orbitals, three sp2 hybrid orbitals are formed
• When an s orbital combines with three p
orbitals, four sp3 hybrid orbitals are formed
• The superscript indicates the number of p
orbitals in the blend or mix
• The number of orbitals is conserved: the
number of hybrid orbitals in a set equals the
number of atomic orbitals used to form the
set
(a) sp hybrid orbitals orient at 180º to each other. (b) sp2
hybrid orbitals orient at 120º to each other. (c) sp3 hybrid
orbitals orient at 109.5º to each other.
The VB description of bonding in BCl3. Each B-Cl bond
is formed by the overlap of a half-filled p orbital of
chlorine with an sp2 hybrid orbital on boron. (Only the
half-filled p orbital of each chlorine is shown.)
The bonds in the
ethane molecule. (a)
Overlap of orbitals.
(b) The degree of
overlap of the sp3
orbitals in the
carbon-carbon bond
is not appreciably
affected by the
rotation of the two
CH3- groups relative
to each other around
the bond.
• Molecules with central atoms with more
than four electron domains violate the octet
rule and require d orbitals to form sufficient
orbitals for bonding
• The two most common hybrids involving
the d orbitals are the sp3d and sp3d2 hybrid
orbitals
• The sp3d hybrids point towards the corners
of a trigonal bipyramid and the sp3d2 point
toward the corners of an octahedron
(a) sp3d hybrid orbitals formed by mixing an s, three p, and a
d orbital. (b) sp3d2 hybrid orbitals formed by mixing an s,
three p, and two d orbitals.
• The VSEPR model can be used to obtain
VB descriptions of bonding
– Examples: (1) VSEPR predicts that CH4 is
tetrahedrial, so the molecule must use sp3
hybrid orbitals. (2) VSEPR predicts that SF6 is
octahedral so the molecule must use sp3d2
hybrid orbitals
• Molecules with nonbonding domains can
also be described with hybrid orbitals
• Lone pairs occupy a bit more volume than
bonding electron pairs
The nitrogen atom in
ammonia has one lone
pair of electrons. The
experimental H-N-H
bond angle is 107º.

The oxygen atom in

water has two lone pairs
of electrons and an
experimental H-O-H
bond angle of 104.5º.
• The formation of coordinate covalent bonds
may also be described with hybrid orbitals
• The tetrafluoroborate ion forms when a
fluoride ion forms a coordiante covalent
bond with boron trifluoride
  3
F  BF3  BF (uses an sp hybrid)
4
• Multiple bonding can also be explained
using hybrid orbitals
• Two types of bonds are important
Sigma bonds concentrate electron density along the
line between the atoms joined by the bonds. The bond
can result from overlap of (a) s, (b) p, or (c) hybrid
orbitals.
Pi bonds form when two p orbitals overlap sideways
instead of end-to-end. The electron density is concentrated
in two regions on opposite sides of the bond axis.
• Multiple bonds almost always consist of a
single sigma bond and one or more pi bonds
• The pi bonds are formed from the p orbitals
that are not involved in the hybrid orbitals
• Hydrocarbons frequently involve pi bonds
• The double bond in alkenes is comprised of
one sigma and one pi bond; the triple bond
in alkynes consists of one sigma and two pi
bonds
The carbon-
carbon
double
bond in
ethene. The
carbon-
carbon
double
bond
consists of
one sigma
and one pi
bond.
(a) the sp hybrid
orbitals on each
carbon form the
sigma bond in
acetylene
(ethyne). (b)
sideways
overlap of the
2px and 2py
orbitals form
two pi bonds. (c)
the pi-bonds
after they form.
• Groups connected by single bonds can
freely rotate
• Rotation is restricted around double bonds
If the CH2 group in front was to
rotate relative to the one in the rear,
the unhybridized p orbitals would
no longer be aligned, meaning the
pi-bond would be broken. Bond
breaking requires more energy than
is available through normal
bending and stretching at room
temperature.
• VB theory can be summarized:
1) The basic framework of the molecule is
determined by the arrangement of the sigma-
bonds
2) Hybrid orbitals are used to form the sigma-
bonds and the lone pairs of electrons
3) The number of hybrid orbitals needed by an
atom in a structure equals the number of
atoms to which it is bonded plus the number
of lone pairs of electrons in its valence shell
 4) When there is a double bond in a molecule, it
consists of one sigma and one pi bond
5) When there is a triple bond, it consists of one
sigma and two pi bonds
• Molecular orbital (MO) theory takes the
the view that a molecule is similar to an
atom
• The molecule has molecular orbitals that
can be populated by electrons just like the
atomic orbitals in atoms
• Like for hybrid orbitals, the number of MOs
formed by combining atomic orbitals is
always equal to the number of atomic
orbitals combined
• In bonding MOs the electron density builds
up between the nuclei
• Electrons in bonding MOs tend to stabilize
a molecule
• In antibonding MOs cancellation of the
electron waves reduces the electron density
between nuclei
 • Antibonding MOs tend to destabilize a
molecule when occupied by electrons

The interaction of the two 1s orbitals on hydrogen can combine

to from one bonding ( 1s ) and one antibonding
( 1s* ) MO. These
are sigma orbitals because the electron density is concentrated
along the imaginary line that passes through both nuclei.
• Bonding MOs are lower in energy than
antibonding MOs
• This can be represented using energy-level
diagrams

MO energy-level diagrams for H2 and He2. The bond order is

one (1) for H2 and zero (0) for He2.
• MOs follow the same filling rules as
atomic orbitals:
1) Electrons fill the lowest-energy orbitals that
are available
2) No more than two electrons, with spin paired,
can occupy any orbital
3) Electrons spread out as much as possible,
with spins unpaired, over orbitals that have
the same energy
The approximate relative energies of molecular orbitals in
second period diatomic molecules. (a) Li2 through N2, (b) O2
through Ne2.
• MO theory correctly predicts the unpaired
electrons in O2 while VB theory does not
• MO theory handles easily the things that
VB theory has trouble with
• MO theory is a bit difficult because even
simple molecules require extensive
calculations
• MO theory describes “resonance” very
efficiently
The sigma (a) and pi (b) framework of benzene. The double
donut – shaped electron cloud (c) formed by the pi-electrons.
In MO terms, the electrons are delocalized and the extra
stability is the delocalization energy. Functionally, the
resonance and delocalization energy are the “same”.