Noncovalent Molecular Forces

What are noncovalent molecular forces? Attractive or repulsive forces between

atoms and/or molecules, other than covalent bonding.
Examples of noncovalent molecular forces include:
- Anion-cation Interaction (Strong force): A noncovalent (van der Waals) attractive
force caused by electrostatic (opposite charge) attraction between an anion and a
cation. Also called by the less precise name ionic force.
EN = 3.0-0.9
= 2.1
This is considered
a slightly ionic
bond.

- Dipole-dipole Interaction (Medium force): A noncovalent (van der Waals) attractive

force caused by alignment of bond dipoles with opposite charges

EN= 4.0-2.8
= 1.2
This bond is
considered polar
covalent, not ionic.

The BrF molecule is slightly

negative at the fluorine, and
thus, a dipole moment is formed
towards the F. When the slightly
positive Br finds a slightly
negative F, a dipole-dipole
interaction takes place.

- Hydrogen Bonding (Strong force): A noncovalent (van der Waals) attractive force
caused by electrostatic attraction of a hydrogen atom with a lone pair of another atom.
The hydrogen bond donor must have a sufficiently large +charge caused by bonding
to a highly electronegative element (O, N, or F; or in uncommon cases by
strongelectron-withdrawing inductive effects). The hydrogen bond acceptor must have
a lone pair, and sufficiently high
electron density
(the accepting
In hydrogen bonding,
atom must have
there are still dipole-dipole
a negative formal
moments; however,
charge, or if
hydrogen bonding is still
neutral must be
the strongest force, so it is
oxygen or
given priority.
nitrogen).

- London Force (Extremely Weak force): A noncovalent molecular force caused by

attraction of polarized electron clouds. The electron cloud polarization is induced: it is
caused when the electron clouds repel each another, creating adjacent regions of
electron deficiency (+) and electron excess (-). It has also been suggested the
polarizations result from random fluctuations in electron density.

- Ion-dipole (Rare force): A noncovalent attraction between one pole of a bond dipole
and an oppositely-charged ion. The +end of the bond dipole is attracted to an anion,
and the - end of the bond dipole is attracted to a cation.

- Cation-pi (Rare force): A noncovalent attractive force between a cation and a pi

electron cloud, usually the pi electron cloud of an aromatic ring.

- Pi Stacking (Rare force): A noncovalent attractive force between two aromatic rings.
Alignment of positive electrostatic potential on one ring with negative electrostatic
potential on another ring forms an offset stack, or in pure benzene, a T-shaped stack.
Also called pi stacking but this label is misleading because it implies that stacking
might occur in any structure with pi electrons.

How to Determine Which Noncovalent Forces Are Operating

What is the EN
of your
molecule?
0.0-0.4: Nonpolar
Covalent

1.8-2.2: Slightly Ionic Bond

2.3-3.3: Highly Ionic Bond
0.5-0.9: Slightly Polar Covalent
1.0-1.3: Moderately Polar Covalent
Bond
1.4-1.7: Highly Polar Covalent

The
attraction
forces are
ionic.

Does the molecule have

polar forces (+/- on the
atoms)?

Yes, there are dipoles present in the

molecules, creating attraction forces
between the molecules.

There is a dipoledipole attraction

present.

Reminder: The strongest

force dominates when one
or more forces are
possible.

Does the
molecule have
electrons? (The
answer is yes.)

London Forces
contribute to the
noncovalent molecular
forces.

No. This molecule

most probably has
only London Forces.

If the dipole-dipole molecule

has a hydrogen bond acceptor
and donor, a lone pair, and any
small, neutral atom or an anion,
the bond also experiences the
attractive forces of hydrogen
bonding.

Ranking of Noncovalent Molecular Forces

Strongest:
- Cation-anion
(ionic
bonds)
- Covalent
bonds

Medium Forces:
- Dipole-dipole
- Hydrogen bonding
- Ion-dipole
- Cation-pi
- Pi-stacking

Weakest:
- London
forces

Sources
Definitions from Dr. Hardingers Online Illustrated Glossary
Images and explanations from Dr. Hardingers Lecture Supplement and Thinkbook