Chapter 2 Molecular Structure and Bonding

1. Lewis structures diagrams that show the pattern of bonds and lone pairs in
a molecule
a. Covalent bond formed when two neighboring atoms share an
electron pair
b. Single bond a shared electron pair (A:B), is denoted A-B
c. Double bond two shared electron pairs (A::B), is denoted A=B
d. Triple bond - three shared pairs of electrons (A:::B)
e. Lone pair an unshared pair of valence electrons on an atom (A:)
i. Lone pairs do not contribute directly to the bonding, they do
influence the shape of the molecule and play an important role
in its properties
f. The octet rule
i. Lewis found that he could account for the existence of a wide
range of molecules by proposing the octet rule: each atom
shares electrons with neighboring atoms to achieve a total of
eight valence electrons (an octet)
1. Decide on the number of electrons that are to be included
in the structure by adding together the numbers of all the
valence electrons provided by the atoms
2. Write the chemical symbols of the atoms in the
arrangement that shows which atoms are bonded
together, less electronegative element is usually the
central atom of a molecule
3. Distribute the electrons in pairs so that there is one pair of
electrons forming a single bond between each pair of
atoms bonded together, and then supply electron pairs (to
form lone pairs of multiple bonds) until each atom has an
octet
g. Resonance
i. Resonance - when the actual structure of the molecule is taken
to be a superposition, or average of all the feasible Lewis
structures corresponding to a given atomic arrangement
ii. Resonance should be pictured as a blending of the structures,
not a flickering alternation between them
iii. The blended structure of two or more structures is called a
resonance hybrid
1. Resonance does not occur between structures in which
the atoms themselves lie in different positions
iv. Resonance has two main effects:
1. Averages the bond characteristics over the molecule
2. The energy of a resonance hybrid structure is lower than
that of any single contributing structure
h. Formal Charge
i. An atom owns all of its nonbonding electrons and half of its
bonding electrons

ii. Formal charge the charge an atom would have if the bonding
electrons were shared equally
1. F.C. = # valence electrons (# unshared electrons + #
shared electrons)
a. Smaller formal charges are preferable to larger
charges
b. Avoid like charges on adjacent atoms
c. A more negative formal charge should exist on an
atom with larger EN value
2. The VSEPR model
a. Valence shell electron pair repulsion (VSEPR) based on some
simple ideas about electrostatic repulsion and the presence or absence
of lone pairs
b. Bonding pairs, lone pairs, or the concentrations of electrons associated
with multiple bonds, take up positions as far apart as possible so that
the repulsions between them are minimized
c. To achieve lowest energy, these regions take up positions as far apart
as possible, so we identify the basic shape
d. We note which locations correspond to atoms and identify the shape of
the molecule
i. The model is highly successful, but sometimes runs into
difficulty when there is more than one basic shape of similar
energy
ii. Repulsions
1. Lone pair/lone pair > lone pair/bonding region > bonding
region/bonding region

3. Valence bond theory a covalent bond forms when the orbitals of two
atoms overlap and the overlap region, which is between the nuclei is
occupied by a pair of electrons
a. A set of overlapping orbitals have a maximum of two electrons that
must have opposite spins
b. The greater the orbital overlap, the stronger (more stable) the bond
c. The valence atomic orbitals in a molecule are different from those in
isolated atoms
d. There is a hybridization of atomic orbitals to form molecular orbitals
e. Hybrid orbitals
i. The number of hybrid orbitals obtained equals the number of
atomic orbitals mixed
ii. The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed
f. Types of Hybrid orbitals
i. Sp, sp2, sp3, sp3d, sp3d2
4. Molecular orbital theory obtained by combing the atomic orbitals on the
atoms in the molecule. Molecular orbitals are wave functions giving the
probability of finding an electron in certain regions of a molecule. Each orbital
can have 2 electrons, each with an opposite spin
a. Sigma bond electron pair in a hybrid orbital is concentrated along
the bond axis and is symmetrically about it, signifies that the orbital
has cylindrical symmetry
b. Pi bond the extra electron pairs in double and triple bonds are
located in un-hybridized atomic orbitals which are not concentrated
along the bond axis. They are located above and below the axis
c. Pauli exclusion principle limits to two the number of electrons that
can occupy any molecular orbital and requires that those two electron
to be paired
d. Bonding orbital arises from the constructive interference of
neighboring atomic orbitals
e. Anti-bonding orbital arises from their destructive interference, as
indicated by a node between the atoms
f. Nonbonding orbital occupation of this orbital neither stabilized nor
destabilizes the molecule
g. Bond order (# electrons in bonding orbitals - # electrons in antibonding orbitals)
i. Bond enthalpy increase a bond order increases
ii. Bond length decreases as bond order increases