VSEPR: Valence Shell Electron Pair Repulsion

Going back to the basics: The rule is that like charges repel each other. For example, electrons tend to repel
each other, and if there were 2 electron pairs, those two pairs will also repel each other based on the rule stated
above. Thus, within a molecule, electrons pairs will orient themselves such that there is maximum separation
between them, which will lead to minimal repulsions. This desire to achieve minimum repulsions between
electron pairs results in various shapes of molecules.

The VSEPR model was developed by Ronald J. Gillespie and R.S. Nyholm and is based on 3 main ideas:

1. Chemical reactions and bonding involve only the electrons in the outermost or valence shell of an atom.
2. Electrons in orbitals and in bonds are always in electrons pairs.
3. Electrons repel one another because of like electrical charge.

Terminology: Sometimes the molecules are represented by AX Y, where Y is the # of peripheral atoms. A:
central atom, X: bonded atoms, E: non-bonding electron pairs

Bonding pair (BP): 2 electrons involved in a bond (X)

Lone pair (LP): 2 electrons NOT involved in a bond (E)

A: Central atom of the molecule

VSEPR Notation B or X: Bonding pair of electrons (the
ligand)
E: non-bonding pair of electrons

Rules for using VSEPR theory: each pair of electrons in the valence shell occupies its own region of space
called the domain of the electron pair.

1. The bonding pairs (BP) and lone pairs (LP) move as far apart as possible to minimize electrostatic
repulsions.
2. A LP occupies slightly more volume than a BP
3. Multiple bonds (double and triple) occupy more volume than a single bond.
4. Polar bonds occupy less space at the central atom than non-polar bonds.

Note: VSEPR is only applicable to molecules or molecular ions. It does not apply to ionic compounds.
The number of valence shell electron pairs (electron domains) determine shape:
Bonding AXE Shape Example
pairs notation
2 pairs Linear

3 pairs Trigonal planar

4 pairs Tetrahedral

5 pairs Trigonal bipyramidal

6 pairs Octahedral

Electron Pair Geometry (EPG): total number of electron pairs about the central atom (BP plus LP)

Molecular Shape OR molecular geometry: number of BP versus LP

Example 1: Silicon lies below carbon in group IV of the periodic table and is tetravalent. Predict the electron
pair geometry, molecular shape and AXE notation of Silane, SiH 4, which is a gas used in the preparation of
extremely pure silicon for use in superconductors.

Example 2: Predict the electron pair geometry, molecular shape and AXE notation of the hexachlorophosphate
ion PCl6-1.

Example 3: Predict the electron pair geometry, molecular shape and AXE notation of chloroform CHCl 3, which
was at one time used as an anaesthetic.

1. Lone electron pairs in the valence shell affect the shapes of molecules.

Example: Ammonia
The lone pair is more spread out – it is bulkier than a bonding pair of electrons and takes up more room than a
covalent bond does. A lone pair also affects the bonding angles. It decreases the bond angles by 2 degrees.

Example: Water

Electron pair repulsion magnitudes decrease in the order:

LP – LP > LP – BP > BP –BP

2. VSEPR theory is applicable to molecules with multiple bonds.

We count a double or triple bond as one group of electrons connecting the ligand X to the central atom A.

Carbon dioxide is classified as an AX 2. Thus its molecular shape is linear.

What about HCN?

Predict the shape of formaldehyde: H2CO

Although, multiple bonds repel single bonds and thus multiple bonds act like lone pairs. Generally, we are
going to treat a double or triple bond as a single electron pair and predict its shape using the rules applied for
single bonded species.
 3. Lone pair electrons occupy the equatorial faces of trigonal bipyramidal molecule.

Placing the lone pair at an equatorial vertex rather than an axial vertex minimizes repulsion due to lone pairs.

AX4E AX3E2 AX2E3

4. Two lone pairs occupy opposite vertices in an octahedron

AX6 AX5E AX4E2 AX3E3

To minimize the lone pair repulsion in AX 4E2 the lone pairs are placed at opposite vertices.

VSEPR Theory: Worksheet

Electron Regions
Compound Lewis Structure Electron Pair Molecular Polar/
Formula (indicate poles!) Geometry Non-Bon Shape Non-Polar?
Bonding
ding

BF3

NH3

NH4+

OCl2
C2H2

VSEPR Theory:
Valence Shell Electron Pair Repulsion Theory

Regions
Regions
Total # of Not
Involved
Bonding Electron Pair Geometry Involved Molecular Geometry
in
Regions in
Bonding
Bonding

2 2 0

Linear Linear

3 0

3 Trigonal Planar

2 1

Trigonal Planar Bent

4 0

4 Tetrahedral

3 1

Trigonal Pyramidal
 2 2

Tetrahedral Bent

Regions
Regions
Total # of Not
Involved
Bonding Electron Pair Geometry Involved Molecular Geometry
in
Regions in
Bonding
Bonding

5 0

Trigonal Bipyramidal

4 1

Distorted
5 Tetrahedral (SeeSaw)

3 2

T-Shaped

2 3

Trigonal Bipyramidal Linear

 Regions
Regions
Total # of Not
Involved
Bonding Electron Pair Geometry Involved Molecular Geometry
in
Regions in
Bonding
Bonding

6 0

Octahedral

6
5 1

Square Pyramidal

4 2

Octahedral Square Planar

The Effect of Non-Bonding Electrons

& Multiple Bonds on Bond Angles

Consider:
 Methane Ammonia Water

🡪domains for non-bonding e- pairs exert greater repulsive forces on adjacent e- domains and thus tend to
compress the bond angles.

Formaldehyde

🡪e- domains for multiple bonds exert a greater repulsive force on adjacent e- domains and thus tend to compress
bond angles.

The VSEPR Theory

& Complex Molecules

The VSEPR Theory can be extended beyond simple molecules.

Consider:
 Acetic Acid
C1 🡪 has 4 bonding regions and all 4 regions are involved in bonding, therefore it will be tetrahedral.
C2 🡪 has 3 bonding regions and all 3 are involved in bonding, therefore it will be trigonal planar.
O(main chain) 🡪 has 4 bonding regions but only 2 are involved in bonding, therefore it will be bent.