Petrucci’s General Chemistry
P R I N C I P L E S A N D M O D E R N A P P L I C AT I O N S
Twelfth Edition
PETRUCCI HERRING MADURA BISSONNETTE
11
Chemical Bonding II:
Valence Bond and
Molecular Orbital Theories
Chemical Bonding II: CONTENTS
Valence Bond and 11-1 What a Bonding Theory Should Do
Molecular Orbital 11-2 Introduction to the
Theories Valence-Bond Method
11-3 Hybridization of Atomic Orbitals
11-4 Multiple Covalent Bonds
11-5 Molecular Orbital Theory
11-6 Delocalized Electrons:
An Explanation Based on
Molecular Orbital Theory
11-7 Some Unresolved Issues:
Can Electron Charge-Density
Plots Help?
11-1 What a Bonding Theory Should Do
FIGURE 11-1
Type of interactions between two hydrogen atoms
FIGURE 11-2
Energy of interaction of two hydrogen atoms plotted for internuclear
separations from zero to infinity
The Covalent Bond: A Quantum
Mechanical Concept
Figure 11-3
Redistrubution of electron density for bond formation in H2
11-2 Introduction to the
Valence-Bond Method
Overlap of half-filled atomic orbital overlap normally
describes covalent bonding.
Sometimes involves the overlap of a filled orbital on one atom
with an empty orbital on another.
A localized electron model of bonding.
FIGURE 11-4
Bonding in H2S represented by atomic orbital overlap
11-3 Hybridization of Atomic Orbitals
The algebraic combination of wave functions is a linear combination of atomic orbitals
FIGURE 11-7
The sp3 hybridization scheme
FIGURE 11-8
Bonding and structure of CH4
A useful representation of the sp3 hybridization of the
valence-shell orbitals of carbon is
Bonding in H2O and NH3
Notice that hybrid orbitals can
accommodate lone-pair
electrons as well as bonding
electrons.
FIGURE 11-9
sp3 hybrid orbitals and bonding in NH3
sp2 Hybrid Orbitals
FIGURE 11-10
The sp2 hybridization scheme
sp Hybridization
FIGURE 11-11
The sp hybridization scheme
sp3d and sp3d2 Hybridization
FIGURE 11-12
The construction of sp hybrid orbitls
FIGURE 11-13
sp3d and sp3d2 hybrid orbitals
Hybrid Orbitals and Valence-Shell
Electron-Pair Repulsion (VSEPR) Theory
• Write a plausible Lewis
structure.
• Use VSEPR to predict electron-
group geometry.
• Select the corresponding
hybridization scheme.
FIGURE 11-14
Using electron-group geometry to determine hybrid orbitals
11-4 Multiple Covalent Bonds
Bonding in C2H4
H H
Ethylene has a double bond in its Lewis structure.
C C
VSEPR says trigonal planar at carbon.
H H
FIGURE 11-15
Sigma (σ) and pi (π) bonding in C2
Bonding in C2H2
FIGURE 11-17
σ and π bonding in C2H2
FIGURE 11-19
Bonding in H2CO – a schematic representation
11-5 Molecular Orbital Theory
Atomic orbitals are isolated on atoms.
Molecular orbitals span two or more atoms.
Calculated orbitals for F2
Analysis of the total wave function describing F2 in its lowest energy
state
MO’s are distributed around both nuclei
Linear Combination of Atomic Orbitals
FIGURE 11-21
Computed molecular orbitals of F2
LCAO Linear Combination of Atomic Orbitals.
Ψ1 = φ1 + φ2 Ψ2 = φ1− φ2
• Each MO can be represented mathematically as a (linear) combination of
AO’s
• The total number of MOs is equal to the total number of Aos
• MOs can be classified as bonding, antibonding, or nonbonding
• The electron configuration for the molecule is obtained by placing the
electrons into the MOs in a particular order
FIGURE 11-22
The interaction of two hydrogen atoms according to molecular theory
Bond Order
Stable species have more electrons in bonding orbitals than antibonding.
No. e− in bonding MOs − No. e− in antibonding MOs
Bond Order =
2
Diatomic Molecules of the First-Period
BO = (e–bond – e–antibond )/2
BOH += (1-0)/2 = ½
2
BOH = (2-0)/2 = 1
2
BOHe + = (2-1)/2 = ½
2
BOHe = (2-2)/2 = 0
2
FIGURE 11-23
Molecular orbital diagrams for the diatomic molecules and ions of the first-period elements
Molecular Orbitals of the
Second Period Elements
First period use only 1s orbitals.
Second period have 2s and 2p orbitals available.
p orbital overlap:
End-to end overlap – sigma bond (σ).
Side-to-side overlap– pi bond (π).
FIGURE 11-24
Formation of bonding and antibonding orbitals from 2p orbitals
FIGURE 11-25
The two possible molecular orbital energy-level schemes for diatomic
molecules of the second-period elements
FIGURE 11-26
Molecular orbital occupancy diagrams for the homonuclear diatomic
molecules of the second-period elements
Experiment shows C2 to be diamagnetic, supporting a
modified energy-level diagram
Expected MO Diagram for C2
Modified MO Diagram for C2
A Special Look at O2
FIGURE 10-3
Paramagnetism of Oxygen
A Look at Heteronuclear Diatomic Molecules
FIGURE 11-27
The relative energies of 2s and 2p orbitals of some second-period elements
FIGURE 11-28
The molecular orbital diagram of CO
11-6 Delocalized Electrons: An Explanation
Based on Molecular Orbital Theory
Bonding in the Benzene Molecule
Dame Kathleen Lonsdale
FIGURE 11-29
Resonance in the benzene molecule and the Kekulé structures
FIGURE 11-30
Bonding in benzene, C6H6, by the valence-bond method
FIGURE 11-31
π molecular orbital diagram for C6H6
Other Structures with Delocalized
Molecular Orbitals
FIGURE 11-32
Structure of the ozone molecule, O3
FIGURE 11-33
π Bonding orbitals of the ozone molecule O3
Extended π systems
FIGURE 11-35
The formation of π molecular orbitals in a long-chain polyene