Theories of Covalent Bonding

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 Theories of Covalent Bonding

11.1 Valence Bond (VB) Theory and Orbital Hybridization

11.2 The Mode of Orbital Overlap and the Types of

Covalent Bonds

11.3 Molecular Orbital (MO)Theory and Electron Delocalization

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 The Central Themes of VB Theory

Basic Principle

A covalent bond forms when the orbitals of two atoms overlap

and are occupied by a pair of electrons that have the highest
probability of being located between the nuclei.

Themes

A set of overlapping orbitals has a maximum of two electrons

that must have opposite spins.
The greater the orbital overlap, the stronger (more stable) the
bond.
The valence atomic orbitals in a molecule are different from
those in isolated atoms.

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 Orbital overlap and
Hydrogen, H2 spin pairing in three
diatomic molecules

Hydrogen fluoride, HF

Fluorine, F2

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 Hybrid Orbitals

Key Points

The number of hybrid orbitals obtained equals the number of

atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed.

Types of Hybrid Orbitals

sp sp2 sp3 sp3d sp3d2

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 The sp hybrid orbitals in gaseous BeCl2

atomic
orbitals

hybrid
orbitals

orbital box diagrams

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 The sp hybrid orbitals in gaseous BeCl2(continued)

orbital box diagrams with orbital

contours

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 The sp2 hybrid orbitals in BF3

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 The sp3 hybrid orbitals in CH4

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 The sp3 hybrid orbitals in NH3

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 The sp3 hybrid orbitals in H2O

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 The sp3d hybrid orbitals in PCl5

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 The sp3d2 hybrid orbitals in SF6

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1-14
 The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

Step 1 Step 2 Step 3

Molecular shape
Molecular Lewis and e- group Hybrid
formula structure arrangement orbitals

Figure 10.1 Figure 10.12 Table 11.1

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 SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

PROBLEM: Use partial orbital diagrams to describe mixing of atomic

orbitals on the central atoms leads to hybrid orbitals in each of
the following:
(a) Methanol, CH3OH (b) Sulfur tetrafluoride, SF4

PLAN: Use the Lewis structures to ascertain the arrangement of

groups and shape of each molecule. Postulate the hybrid
orbitals. Use partial orbital box diagrams to indicate the hybrid
for the central atoms.

SOLUTION: (a) CH3OH H The groups around C are

C O arranged as a tetrahedron.
H H H
O also has a tetrahedral
arrangement with 2 nonbonding
e- pairs.

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 SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

continued

2p 2p
sp3 sp3
hybridized hybridized
2s single C atom 2s single O atom
C atom O atom

(b) SF4 has a seesaw shape with 4 bonding and 1 nonbonding e- pairs.
F
F S
F 3d 3d
F

3p
sp3d
hybridized
S atom
3s S atom

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 The s bonds in ethane.

both C are sp3

hybridized s-sp3 overlaps to s
bonds

sp3-sp3 overlap to form a s

bond relatively even
distribution of
electron density over
all s bonds

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 The s and p bonds in ethylene (C2H4)

overlap in one position -

s

p overlap - p

electron
density
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 The s and p bonds in acetylene (C2H2)

overlap in one position -

s

p overlap - p

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 SAMPLE PROBLEM 11.2 Describing the Bonding in Molecules with
Multiple Bonds
PROBLEM: Describe the types of bonds and orbitals in acetone, (CH3)2CO.

PLAN: Use the Lewis structures to ascertain the arrangement of groups and
shape at each central atom. Postulate the hybrid orbitals taking note of
the multiple bonds and their orbital overlaps.

SOLUTION: sp2 sp2

sp3 hybridized
O
O
O sp2
H H
sp3 hybridized H C H sp 2
sp3
C C
H sp3 2
H H
H sp2 C sp C sp3 C
C H
sp2 hybridized 3 sp3 H3 C CH3
3
sp H sp 3H
H sp3 sp

pbond
sbonds
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 Restricted rotation of p-bonded molecules

CIS
TRANS

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 The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.

Atomic wave functions are summed to obtain molecular wave

functions.

If wave functions reinforce each other, a bonding MO is formed

(region of high electron density exists between the nuclei).

If wave functions cancel each other, an antibonding MO is formed

(a node of zero electron density occurs between the nuclei).

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 An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of wave
functions
1-24 subtracted.
 Contours and energies of the bonding and antibonding
molecular orbitals (MOs) in H2.

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 The MO diagram for H2

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 MO diagram for He2+ and He2

s*1 s*1
s s
Energy

Energy
1s 1s 1s 1s

s1s s1s
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He

He2+ bond order = 1/2 He2 bond order = 0

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 SAMPLE PROBLEM 11.3 Predicting Species Stability Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

PLAN: Use H2 as a model and accommodate the number of electrons in

bonding and antibonding orbitals. Find the bond order.

SOLUTION:
bond order bond order
= 1/2(1-0) = 1/2(2-1)
= 1/2 = 1/2
s s
+
H2 does exist H2- does exist

1s 1s 1s 1s

AO of H AO of H AO of H-
AO of H
s s configuration is
configuration is (s1s)1 (s1s)2(s2s)1
MO of H2 + MO of H2-

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 s*2 s*2
s s

2s 2s 2s 2s
Energy

Bonding in s-block Be2

Li2 s2s
s2s homonuclear
diatomic
molecules.

s*1 s*1
s s

1s 1s 1s 1s

Li2 bond order = 1 Be2 bond order = 0

s1s s1s
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 Contours and energies of s and p MOs through
combinations of 2p atomic orbitals

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 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.
without 2s-2p with 2s-2p
mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2

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MO occupancy and
molecular
properties for B2
through Ne2

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 The paramagnetic
properties of O2

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 SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

PROBLEM: As the following data show, removing an electron from N2 forms

an ion with a weaker, longer bond than in the parent molecules,
whereas the ion formed from O2 has a stronger, shorter bond:
N2 N2+ O2 O 2+

Bond energy (kJ/mol) 945 841 498 623

Bond length (pm) 110 112 121 112

Explain these facts with diagrams that show the sequence and occupancy of MOs.

PLAN: Find the number of valence electrons for each species, draw the MO
diagrams, calculate bond orders, and then compare the results.

SOLUTION:

N2 has 10 valence electrons, so N2+ has 9.

O2 has 12 valence electrons, so O2+ has 11.

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 SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

continued
N2 N2+ O2 O2 +

s2p s2p antibonding

e- lost
bonding e- lost p2p p2p

s2p s2p

p2p p2p

s2s s2s

s2s s2s

1/2(8-2)=3 1/2(7-2)=2.5 bond 1/2(8-4)=2 1/2(8-3)=2.5

orders

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 The lowest energy p-bonding MOs in benzene and ozone.

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 The MO diagram for HF

s

Energy

1s

2px 2py 2p

s
AO MO of AO
of H HF of F
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 s* The MO diagram for NO
s

p* p
Energy

2p
s 2p
p
possible Lewis
structures
p p 0 0
N O
s* s -1 +1
2s N O
2s
AO of N AO of O
s s

MO of NO
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 The steps in converting a molecular formula into a Lewis structure.

Place atom
Molecular
Step 1 with lowest
formula
EN in center
Atom Add A-group
Step 2
placement numbers

Sum of Draw single bonds.

Step 3
valence e- Subtract 2e- for each bond.
Give each
Remaining
Step 4 atom 8e-
valence e-
(2e- for H)

Lewis
structure

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 The steps in determining a molecular shape.

See Figure
Molecular
Step 1 10.1
formula

Lewis Count all e- groups around central

Step 2
structure atom (A)

Electron-group Note lone pairs and double

Step 3
arrangement bonds
Count bonding and
Bond
Step 4 nonbonding e-
angles
groups separately.

Molecular
shape
(AXmEn)

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