Chapter 9.

Molecular Geometry & Bonding Theories

VSEPR THEORY – Valence shell electron pair repulsion theory
• Structure of molecule is largely determined by repulsions between electron
domains; molecule adopts structure that minimizes repulsions.
electron domain – region occupied by
1) bonding electrons (single or multiple bond) or
2) nonbonding electrons (lone pair)
Electron pair geometry is determined by the total number of electron groups
around central atom. Table 9.1 gives the electron pair geometries and associated
bond angles for molecules where the central atom is surrounded by 2-6 groups of
electrons. (Textbook calls this electron domain geometry.)
Molecular geometry describes the actual shape of the molecule.
• If central atom does not have lone pairs, molecular geom = e- domain
geometry
• If central atom has lone pairs, molecular geometry is different than e- domain
geometry. (Lone pairs still occupy space & exert repulsive force on bonds.)
• Note that a multiple bond is counted as 1 e- group, since a multiple bond
exerts 1 repulsion & occupies 1 region in space. E.g. O=C=O is linear
Total # e- e- pair geometry # bonded # of lone molecular geometry E.g.
groups atoms pairs around
around central atom
central atom
2 linear 2 0 linear CO 2
3 trigonal planar 3 0 trigonal planar SO3
3 2 1 bent NO2 -
4 tetrahedral 4 0 tetrahedral CH4
4 3 1 trigonal pyramid NH3
4 2 2 angular (bent) H2 O
5 trigonal 5 0 trigonal bipyramid PF5
5 bipyramid 4 1 seesaw SF4
5 3 2 T-shape ClF3
5 2 3 linear XeF2
6 octahedral 6 0 octahedral SF6
6 5 1 square pyramidal BrF 5
6 4 2 square planar XeF4
Since lone pairs of electrons are not shared, they exert a larger repulsive force on
bonding e- pairs:
1) This pushes atoms together so molecules have smaller bond angles than
expected. e.g. For water the bond angle is 104.5°, not 109.5°.
2) Lone pairs prefer to occupy positions where they have more space to
minimize electron-electron repulsions.
A. 5 groups around central atom: lone pairs occupy positions in planar
triangle. e.g. seesaw, T-shape, linear
B. 6 groups around central atom: 2 lone pairs occupy opposite positions.
e.g. square planar
MOLECULAR POLARITY
• Not all molecules with polar bonds are polar, it also depends on symmetry.
A molecule is polar if it has polar bonds and
1) structure is not symmetrical – usually central atom has lone pairs.
2) different atoms are bonded to the central atom.
E.g. H2 O, CH3 F
Molecule is nonpolar if
1) symmetrical structure where non-central atoms are identical;
symmetrical structures: linear, trigonal planar, tetrahedral, trigonal bipyramid,
octahedral, square planar
2) all bonds are nonpolar.
• Nonpolar molecules are usually very symmetrical, center of +/- charge
coincides
E.g. O=C=O, BF3
Exercise. For Lewis Structure worksheet determine the a) molecular geometry; b)
label molecules as polar or nonpolar.
VALENCE BOND THEORY
A model that pictures covalent bond formation as the overlap of two singly
occupied atomic orbitals.

H2

HF

sigma bond, σ , forms by end on overlap of two atomic orbitals. Electron density
lies on axis between atoms (internuclear axis).
• A single bond is a sigma bond.

pi bond, π , forms by the sideways overlap of two p orbitals. The overlap region
lies above and below the internuclear axis.
• Double bond has 1 sigma and 1 pi bond
• Triple bond has 1 sigma and 2 pi bonds

Hybridization – mixing of atomic orbitals so that equivalent bonds can form.

# e- groups e- pair geometry Hybridization E.g.

2 linear sp CO 2 , HCN
3 trigonal planar sp2 BF3 , SO 3
4 tetrahedral sp3 CH4 , H2 O
5 trigonal bipyramid sp3 d PCl 5 , I3
-

6 octahedral sp3 d2 XeF4 , SF6

sp3 hybridization
E.g. CH4 ; C has 4 electrons in its valence shell. This shell has one 2s orbital and
three 2p orbitals.
å ææç → æ æææ → ææææ
2s 2p e- promotion 2s 2p hybridization 2sp3
4 bonding sites 4 equivalent
orbitals
Hybridization involves mixing of one 2s and three 2p orbitals → four sp3 orbitals
are formed. This allows better overlap between sp3 orbital of C & 1s orbital of H -
- stronger bonds & more stable molecules form.
• Each C-H bond is a sigma bond (σ) - involves overlap of sp3 -s orbitals
sp2 hybridization
E.g. ethylene CH2 =CH2
å ææç → æææ æ
2s 2p promote & hybridize 2sp2 2p
• one 2s & two 2p orbitals mix → 3 sp2 orbitals (σ bonds)
• p orbital forms π bond (side-to-side overlap of p orbitals)
• each C=C bond: one σ (sp2 -sp2 ) & one π bonds (2p-2p)
• sp2 orbitals form 120° <'s – trigonal planar geometry
sp hybridization
H-C≡≡ C-H
å ææç → ææ ææ
2s 2p promote & hybridize 2sp 2p
• Each C has 2 sp orbitals; two 2p orbitals
• Each triple bond one σ (sp-sp) & two π (p-p) bonds
• Geometry is linear w/ 180° bond angles

Problem. For the following structure

CH3 -CH=CH-C≡N
1 2 3 4

1) Give the hybridization for: C sp3 C 2 sp2 C 4 sp N sp

2) How many sigma and pi bonds are present in the structure?

sigma bonds 9 pi bonds 3

3) What are the bond angles for C 1 109.5° C 2 120° C 4 180°