Chemical Bonding II:

Molecular Geometry and

Hybridization of Atomic Orbitals
Chapter 10
1
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Valence shell electron pair repulsion (VSEPR) model:

Predict the geometry of the molecule from the electrostatic

repulsions between the electron (bonding and nonbonding)
pairs.
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

2 0 linear linear

2
Beryllium Chloride

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 VSEPR

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
2 0 linear Linear
trigonal
trigonal
3 0 Planar
planar

4
Boron Trifluoride

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 VSEPR (2)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
2 0 linear linear

3 0 trigonal trigonal
planar planar

4 0 tetrahedral tetrahedral

6
 Methane

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 VSEPR (3)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
2 0 linear linear

3 0 trigonal trigonal
planar planar
4 0 tetrahedral tetrahedral

5 0 trigonal trigonal
bipyramidal bipyramidal

8
Phosphorus Pentachloride

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 VSEPR (4)

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
2 0 linear linear
3 0 trigonal trigonal
planar planar
4 0 tetrahedral tetrahedral

5 0 trigonal trigonal
bipyramidal bipyramidal
6 0 Octahedral octahedral

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Sulfur Hexafluoride

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 Summary of VSEPR

*Bonds coming out of the page are represented as solid wedges. Bonds going into the page are represented as
dashed wedges.
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 Tetrahedral Bond Angles

repulsion ¿
lone-pair vs. lone-pair
pair repulsion ¿
lone-pair vs. bonding- bonding-pair vs. bonding-
13
pair repulsion
 VSEPR: 3 Electron Groups
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
3 0 trigonal trigonal
Planar planar
2 1 trigonal bent
planar

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 VSEPR: 4 Electron Groups

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
4 0 tetrahedral tetrahedral
3 1 tetrahedral trigonal
pyramidal

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 VSEPR: 4 Electron Groups (2)

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
4 0 tetrahedral tetrahedral

3 1 tetrahedral trigonal
pyramidal
2 2 tetrahedral bent

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 VSEPR: 5 Electron Groups
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
5 0 trigonal trigonal
bipyramidal bipyramidal
4 1 trigonal distorted
bipyramidal tetrahedron

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 VSEPR: 5 Electron Groups (2)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
5 0 trigonal trigonal
bipyramidal bipyramidal
4 1 trigonal distorted
bipyramidal tetrahedron
3 2 trigonal T-shaped
bipyramidal

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 VSEPR: 5 Electron Groups (3)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
5 0 trigonal trigonal
bipyramidal bipyramidal
4 1 trigonal distorted
bipyramidal tetrahedron
3 2 trigonal T-shaped
bipyramidal
2 3 trigonal linear
bipyramidal

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 VSEPR: 6 Electron Groups
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
6 0 octahedral octahedral
5 1 octahedral square
pyramidal

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 VSEPR: 6 Electron Groups (2)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
6 0 octahedral octahedral

5 1 octahedral square
pyramidal
4 2 octahedral square
planar

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21
Summary of Molecular Shapes

22
Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.

23
Example 10.1
Use the VSEPR model to predict the geometry of the following
molecules and ions:

(a)
Example 10.1 (1)
Strategy The sequence of steps in determining molecular
geometry is as follows:

draw Lewis
structure
⟶ find arrangement of
electron pairs ⟶ find arrangement
of bonding pairs
⟶ based
determine geometry
on bonding pairs

Solution
(a) The Lewis structure of is

There are four electron pairs around the central atom;

therefore, the electron pair arrangement is tetrahedral
(see Table 10.1).
Example 10.1 (2)
Recall that the geometry of a molecule is determined only
by the arrangement of atoms (in this case the As and H
atoms). Thus, removing the lone pair leaves us with three
bonding pairs and a trigonal pyramidal geometry, like . We
cannot predict the HAsH angle accurately, but we know that
it is less than because the repulsion of the bonding electron
pairs in the bonds by the lone pair on As is greater than the
repulsion between the bonding pairs.

(b) The Lewis structure of is

There are four electron pairs around the central atom;

therefore, the electron pair arrangement is tetrahedral.
Example 10.1 (3)
Recall that the geometry of a molecule is determined only by
the arrangement of atoms (in this case the O and F atoms).
Thus, removing the two lone pairs leaves us with two
bonding pairs and a bent geometry, like . We cannot predict
the FOF angle accurately, but we know that it must be less
than because the repulsion of the bonding electron pairs in
the O−F bonds by the lone pairs on O is greater than the
repulsion between the bonding pairs.

(c) The Lewis structure of is

Example 10.1 (4)
There are four electron pairs around the central atom;
therefore, the electron pair arrangement is tetrahedral.
Because there are no lone pairs present, the arrangement of
the bonding pairs is the same as the electron pair
arrangement. Therefore, has a tetrahedral geometry and
the ClAlCl angles are all .

(d) The Lewis structure of is

There are five electron pairs around the central I atom;

therefore, the electron pair arrangement is trigonal
bipyramidal. Of the five electron pairs, three are lone pairs
and two are bonding pairs.
Example 10.1 (5)
Recall that the lone pairs preferentially occupy the
equatorial positions in a trigonal bipyramid (see Table 10.2).
Thus, removing the lone pairs leaves us with a linear
geometry for , that is, all three I atoms lie in a straight line.

(e) The Lewis structure of is

The bond is treated as though it were a single bond in the

VSEPR model. Because there are three electron pairs
around each C atom and there are no lone pairs present,
the arrangement around each C atom has a trigonal planar
shape like , discussed earlier.
Example 10.1 (6)
Thus, the predicted bond angles in are all .

Comment
(1) The ion is one of the few structures for which the bond
angle can be predicted accurately even though the central
atom contains lone pairs.

(2) In ,all six atoms lie in the same plane. The overall planar
geometry is not predicted by the VSEPR model, but we will
see why the molecule prefers to be planar later. In reality,
the angles are close, but not equal, to because the bonds
are not all equivalent.
 Dipole Moments and Polar Molecules
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𝜇=𝑄 × 𝑟
Q is the charge
r is the distance between charges
− 30 31
1 D= 3.36 × 10 Cm
Behavior of Polar Molecules

32
Bond moments and resultant dipole moments in and .

33
 Dipole Moments of Some Polar Molecules

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Table10.3 Dipole Movements of Some Polar Molecules
Molecule Geometry Dipole Moment (D)
Linear 1.92
Linear 1.08
Linear 0.78
Linear 0.38
Bent 1.87
Bent 1.10
Trigonal pyramidal 1.46
Bent 1.60

34
 Chemistry In Action: Microwave Ovens
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Example 10.2

Predict whether each of the following molecules has a dipole

moment:

(a) (trigonal planar)

(b) (tetrahedral)
Example 10.2 (1)
Strategy
Keep in mind that the dipole moment of a molecule depends on
both the difference in electronegativities of the elements
present and its geometry.

A molecule can have polar bonds (if the bonded atoms have
different electronegativities), but it may not possess a dipole
moment if it has a highly symmetrical geometry.
Example 10.2 (2)
Solution
(a) Because bromine chloride is diatomic, it has a linear
geometry. Chlorine is more electronegative than bromine
(see Figure 9.5), so is polar with chlorine at the negative
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Thus, the molecule does have a dipole moment. In fact, all

diatomic molecules containing different elements possess a
dipole moment.
Example 10.2 (3)
(b) Because fluorine is more electronegative than boron, each
bond in (boron trifluoride) is polar and the three
bond moments are equal. However, the symmetry of a
trigonal planar shape means that the three bond moments
exactly cancel one another:
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An analogy is an object that is pulled in the directions shown

by the three bond moments. If the forces are equal, the
object will not move. Consequently, has no dipole moment;
it is a nonpolar molecule.
Example 10.2 (4)
(c) The Lewis structure of (methylene chloride) is

This molecule is similar to in that it has an overall

tetrahedral shape. However, because not all the bonds are
identical, there are three different bond angles: , , and . These
bond angles are close to, but not equal to, .
Example 10.2 (5)
Because chlorine is more electronegative than carbon,
which is more electronegative than hydrogen, the bond
moments do not cancel and the molecule possesses a
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Thus, is a polar molecule.

Change in Potential Energy of Two Hydrogen Atoms
as a Function of Their Distance of Separation

42
Change in Electron Density as Two Hydrogen Atoms
Approach Each Other

43
 Hybridization

Hybridization – mixing of two or more atomic

orbitals to form a new set of hybrid orbitals

1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p).

Hybrid orbitals have very different shape from original
atomic orbitals.
2. Number of hybrid orbitals is equal to number of pure atomic
orbitals used in the hybridization process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals

44
Formation of Hybrid Orbitals

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Formation of Covalent Bonds in

46
-Hybridized N Atom in
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Predict correct
bond angle

47
Formation of Hybrid Orbitals

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48
Formation of Hybrid Orbitals
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How do I predict the hybridization of the central atom?
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the number of
atoms bonded to the central atom

# of Lone Pairs
+
# of Bonded Atoms Hybridization Examples
2

6 50
Important Hybrid Orbitals

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Example 10.3
Determine the hybridization state of the central (underlined)
atom in each of the following molecules:

Describe the hybridization process and determine the molecular

geometry in each case.
Example 10.3 (1)
Strategy The steps for determining the hybridization of the
central atom in a molecule are:
draw Lewis structure use VSEPR to determine the use Table 10.4 to
of the molecule ⟶ electron pair arrangement ⟶ determine the
surrounding the central atom hybridization state of
(Table 10.1) the central atom

Solution
(a) The ground-state electron configuration of Be is and
the Be atom has two valence electrons. The Lewis structure of
is
Example 10.3 (2)
There are two bonding pairs around Be; therefore, the electron
pair arrangement is linear. We conclude that Be uses sp hybrid
orbitals in bonding with H, because sp orbitals have a linear
arrangement (see Table 10.4). The hybridization process can
be imagined as follows. First, we draw the orbital diagram for
the ground state of Be:

By promoting a electron to the orbital, we get the excited state:

Example 10.3 (3)
The and orbitals then mix to form two hybrid orbitals:

The two bonds are formed by the overlap of the Be sp

orbitals with the orbitals of the H atoms. Thus, is a linear
molecule.
Example 10.3 (4)
(b) The ground-state electron configuration of Al is .
Therefore, the Al atom has three valence electrons. The
Lewis structure of is

There are three pairs of electrons around Al; therefore,

the electron pair arrangement is trigonal planar. We
conclude that Al uses hybrid orbitals in bonding with I
because orbitals have a trigonal planar arrangement.
The orbital diagram of the ground-state Al atom is
Example 10.3 (5)
By promoting a electron into the orbital we obtain the following
excited state:

The and two orbitals then mix to form three hybrid orbitals:

The hybrid orbitals overlap with the orbitals of I to form three

covalent bonds. We predict that the molecule is trigonal planar
and all the angles are .
Example 10.3 (6)
(c) The ground-state electron configuration of P is . Therefore, P
atom has five valence electrons. The Lewis structure of is

There are four pairs of electrons around P; therefore, the

electron pair arrangement is tetrahedral. We conclude that P
uses hybrid orbitals in bonding to F, because orbitals have a
tetrahedral arrangement. The hybridization process can be
imagined to take place as follows. The orbital diagram of the
ground-state P atom is
Example 10.3 (7)
By mixing the and orbitals, we obtain four hybrid orbitals.

As in the case of , one of the hybrid orbitals is used to

accommodate the lone pair on P. The other three hybrid orbitals
form covalent bonds with the 2p orbitals of F. We predict the
geometry of the molecule to be trigonal pyramidal; the angle
should be somewhat less than .
Example 10.4
Describe the hybridization state of phosphorus in phosphorus
pentabromide .
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PBr 5
Example 10.4 (1)
Strategy Follow the same procedure shown in Example
10.3.

Solution The ground-state electron configuration of P

is .Therefore, the P atom has five valence electrons. The Lewis
structure of is

There are five pairs of electrons around P; therefore, the

electron pair arrangement is trigonal bipyramidal. We conclude
that P uses hybrid orbitals in bonding to Br, because hybrid
orbitals have a trigonal bipyramidal arrangement.
Example 10.4 (2)
The hybridization process can be imagined as follows. The
orbital diagram of the ground-state P atom is

Promoting a electron into a orbital results in the following

excited state:
Example 10.4 (3)
Mixing the one , three , and one orbitals generates five hybrid
orbitals:

These hybrid orbitals overlap the orbitals of to form five covalent

bonds. Because there are no lone pairs on the P atom, the
geometry of is trigonal bipyramidal.
Hybridization of Carbon

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64
 Hybridization of Carbon (1)
Unhybridized orbital (gray), which is perpendicular to
the plane of the hybrid (green) orbitals.

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 Bonding in Ethylene,

Sigma bond electron density between the 2 atoms

Pi bond electron density above and below plane of nuclei of

the bonding atoms 66
 Sigma and Pi Bonds

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

67
Another View of Bonding in Ethylene,

68
Hybridization of Carbon

69
Bonding in Acetylene,

70
Another View of the Bonding in Acetylene,

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71
Example 10.5
Describe the bonding in the formaldehyde molecule whose
Lewis structure is

Assume that the O atom is hybridized.

Example 10.5 (1)
Strategy Follow the procedure shown in Example 10.3.

Solution There are three pairs of electrons around the C

atom; therefore, the electron pair arrangement is trigonal
planar. (Recall that a double bond is treated as a single bond in
the VSEPR model.) We conclude that C uses hybrid orbitals in
bonding, because hybrid orbitals have a trigonal planar
arrangement. We can imagine the hybridization processes for C
and O as follows:
Example 10.5 (2)
Carbon has one electron in each of the three orbitals, which
are used to form sigma bonds with the H atoms and the O
atom. There is also an electron in the orbital, which forms a pi
bond with oxygen. Oxygen has two electrons in two of its
hybrid orbitals. These are the lone pairs on oxygen. Its third
hybrid orbital with one electron is used to form a sigma bond
with carbon. The orbital (with one electron) overlaps
with the orbital of C to form a pi bond.
 Experiments Show is Paramagnetic

No unpaired
Should be diamagnetic

Molecular orbital theory – bonds are formed from

interaction of atomic orbitals to form molecular
orbitals. 75
Energy Levels of Bonding and Antibonding Molecular
Orbitals in Hydrogen

A bonding molecular orbital has lower energy and greater

stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and

lower stability than the atomic orbitals from which it was
formed. 76
Constructive and Destructive
Interference

77
Two Possible Interactions Between Two Equivalent p Orbitals

78
Molecular Orbital (MO) Configurations

1. The number of molecular orbitals (MOs) formed is always

equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

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 Molecular Orbital (MO) Configurations (1)

1
bond order = ( Number of electons∈bonding MOs− Number of electrons∈antibonding MOs )
2

bond 1
1
1
2 0
2 80
order
Molecular Orbital (MO) Configurations (2)
General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules , , , , and .

81
 Molecular Orbital (MO) Configurations (3)
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*For simplicity the and orbital are omitted. These two orbital hold a total of four electrons. Remember that for and , , is lower in energy than and

82
Example 10.6
The ion can be prepared by bombarding the molecule with
fast-moving electrons.

Predict the following properties of :

(a) electron configuration

(b) bond order

(c) magnetic properties

(d) bond length relative to the bond length of (is it longer or

shorter?)
Example 10.6 (1)
Strategy From Table 10.5 we can deduce the properties of
ions generated from the homonuclear molecules.

How does the stability of a molecule depend on the number of

electrons in bonding and antibonding molecular orbitals?

From what molecular orbital is an electron removed to form the

ion from N2?

What properties determine whether a species is diamagnetic or

paramagnetic?
Example 10.6 (2)
Solution From Table 10.5 we can deduce the properties of
ions generated from the homonuclear diatomic molecules.

(a)Because has one fewer electron than , its electron

configuration is

(b)The bond order of is found by using Equation (10.2):

bond order

(c) has one unpaired electron, so it is paramagnetic

Example 10.6 (3)
(d) Because the electrons in the bonding molecular orbitals are
responsible for holding the atoms together, should have a
weaker and, therefore, longer bond than . (In fact, the bond
length of is 112 pm, compared with 110 pm for.)

Check Because an electron is removed from a bonding

molecular orbital, we expect the bond order to decrease. The
ion has an odd number of electrons (13), so it should be
paramagnetic.
 Delocalized Molecular Orbitals
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.

Example: Benzene,

Delocalized orbitals

87
 Delocalized Molecular Orbitals (1)

Electron density above and below the plane of the

benzene molecule.

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88
Bonding in the Carbonate Ion,

89
Chemistry In Action: Buckyball Anyone?

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