INTERMOLECULAR

INTERACTIONS

INTRAMOLECULAR INTERACTION

(http://www.chem.ufl.edu/~itl/4411/lectures/lec_g

NTERMOLECULAR INTERACTIONS

(http://www.chem.ufl.edu/~itl/4411/lectures/lec_g.h

Modelling of
Intermolecular Interactions
Intermolec
ular
interaction
Short range
<3
Repulsive

Long range
>3
Attractive
Van der
Waals
interaction

hort Range Repulsive Interaction

When two non-bonded atoms approach
each each other, at some distance
overlap of the occupied orbitals results in
electrostatic repulsion between the
electrons of those atoms.
This repulsive energy acts over a very
short range, but goes up very sharply
when that range is violated.
The repulsion goes up as 1/r12. It is
important only when atoms are in very
close proximity, but then it becomes very

 Because this repulsive term rises so

sharply as distance decreases it is
sometimes reasonable to think of
atoms as hard spheres, like small pool
balls, defined by van der Waals radii
and surfaces.
When two atoms approach each other
their van der Waals surfaces make
contact when the distance between
them reaches the sum of their van der
Waals radii.
Here we are assuming that bonds do
not form. When bonds form van der
Waals radii are violated.

 The van der Waal radius of carbon is

evident from the spacing between the
layers in graphite.
The distance between atoms in
different layers of graphite is never
less than twice the van der Waals
radius of carbon (2 x 1.7 = 3.4 ).
The atoms within a graphite layer are
covalently linked and so are in
violation of the van der Waals radius.

DIPOLE

tp://ww2.chemistry.gatech.edu/~lw26/structure/molecular_interactions/mol_int.h

An electric dipole is a separation of

positive and negative charges

(http://hcxy.wzu.edu.cn/gdwlhx/ShowNews.aspx?
ID=6845&Tid=279)

 Due to non-uniform distributions of

positive and negative charges on the
various atoms, many molecules have
dipole moments.
Such is the case with polar compounds
like water (H2O), where electron
density is shared unequally between
atoms.
The physical chemist Peter J. W. Debye
was the first scientist to study
molecular dipoles extensively.

Dipole moment ():

= ql

(1)

where q : charge
l : distance of positive and negative
charges
Dipole energy:
q2
2
U

40r 40r3

(2)

where 0 : permittivity of vacuum (= 8.854

10-12 F/m)
r : relative permittivity or
dielectric constant of the medium

For molecules there are three types of

dipoles:

1.Permanent dipoles:
These occur when two atoms in a
molecule have substantially different
electronegativity: One atom attracts
electrons more than another,
becoming more negative, while the
other atom becomes more positive. A
molecule with a permanent dipole
moment is called a polar molecule.

2.Instantaneous dipoles:
These occur due to chance when
electrons happen to be more
concentrated in one place than
another in a molecule, creating a
temporary dipole.

(http://www.chemprofessor.com/imf.htm)

3.Induced dipoles:
These can occur when one molecule
with a permanent dipole repels
another molecule's electrons,
inducing a dipole moment in that
molecule. A molecule is polarized
when it carries an induced dipole. See
induced-dipole attraction.

Dipole moment values of some typical gas

phase in debye units are:
Compound
NaCl
CH3Cl
H2O
NH3
CO2
CCl4

Dipole Moment
(Debyes)
9.0
(measured in the
gas phase)
1.87
1.85
1.47
0
0

Ion-Dipole Interaction

(http://www.chem.purdue.edu/gchelp/liquids/iondip.html)

 A dipole that is close to a positive or

negative ion will orient itself so that the
end whose partial charge is opposite to
the ion charge will point toward the ion.
This kind of interaction is very
important in aqueous solutions of ionic
substances.
H2O is a highly polar molecule, so that
in a solution of sodium chloride, the Na+
ions will be enveloped by a shell of
water molecules with their oxygen-ends
pointing toward these ions, while H2O

r
1

r
2

Qq 1 1

U r
40r r1 r2

The interaction
energy can be
constructed from
the Coulomb
interactions
between the bare
charge Q and the
dipolar charges
(3)
q:

r1 r cos sin
2

r2 r cos sin
2

where
Q : charge of ion
r : distance between ion and dipole
0 : permittivity of vacuum (= 8.854
10-12 F/m)
r : relative permittivity or
dielectric constant of the medium
where the charges are located in
l : length of dipole moment vector
: the angle between the dipole
vector
and the vector
Whenmoment
the dipole
is sufficiently
far away
ionl),
with
from connecting
the charge the
(r >>
we the
can dipole
approximate:

r1 r cos
r2 r cos
2
2

he interaction energy is then

Qq
1
1
U r

40r r cos r cos

2
2

Qq
cos

40r 2 2 2
r cos

4
Q cos
U r
2
40rr
where

(4)
(1)

 When deriving eq. (4) we assumed the

dipole to be sufficiently far from the
charge (r >> l).
At about r < 2l the approximation
deviate more than 10% from the exact
result.
Taking into account the finite size of
atoms and molecules, eq. (4) is actually
an excellent approxi-mation for
interactions between ions and small
polar molecules at all physically relevant
distances.
In the case of larger molecules, where

Dipole-Dipole Interaction

(http://2012books.lardbuck
et.org/books/generalchemistry-principlespatterns-and-applicationsv1.0m/section_15_02.html

(http://2012books.lardbucket.o
rg/books/general-chemistryprinciples-patterns-andapplications-

 As two dipoles approach each other,

they will tend to orient themselves so
that their oppositely-charged ends are
adjacent.
Two such arrangements are possible:
the dipoles can be side by side but
pointing in opposite directions, or they
can be end to end.
It can be shown that the end-to-end
arrangement gives a lower potential
energy.
Dipole-dipole attraction is weaker than
ion-dipole attraction, but it can still

for r > 3 l:
1 2
U
1 cos2 sin1 sin2 cos
3 2cos
40rr

(5)

1 and 2 are the polar orientation

angles of 1 and 2, respectively, and is
the azimuthal orientation angle of 2 in

 Dipole-dipole interaction is
comparatively weak (for dipole
moment of 1 Debye at 0.35 nm in
vacuum, the interaction is already
weaker than kT).
In certain molecules (small size and
large dipole moment O-H, N-H, and FH), dipole-dipole interaction can lead
to short range association in liquid
(part of H-bond).
Dipole-dipole interaction is strongest
when the two dipoles mutually orient

 At large separation or in a medium of

high , when interaction falls below kT,
dipoles can now rotate more freely.
The angle averaged potentials are not
zero because of Boltzmann weighting
factor, the energy (Keesom interaction
or orientation interaction) becomes
2 1 1 2

U r
3 kBT 40r
for
1 2
kBT
40rr3

1
r6

(6)

on-Induced Dipole Interaction

Polarizability ()
Polarizability is the ease of distortion of
the electron cloud of a molecular entity
by an electric field (such as that due to
the proximity of a charged reagent).
It is experimentally measured as the
ratio of induced dipole moment ( ind) to

ind
the field
E
induces it:
0 which
(7)
E

 The most significant

induced dipole effects
result from nearby
ions, particularly
cations (positive ions).
Nearby ions can distort the electron
clouds even in polar molecules, thus
temporarily changing their dipole
moments.
The larger ions (especially negative ones
such as SO22 and ClO42) are highly
polarizable, and the dipole moments
induced in them by a cation can play a

pole-Induced Dipole Interaction

induction or Debye interaction)

(http://textbook.s-anand.net/ncert/class-11/chemistry/5-statesof-matter)

 A permanent dipole can induce a

temporary one in a species that is
normally non-polar, and thus produce a
net attractive force between the two
particles.
This attraction is usually rather weak,
but in a few cases it can lead to the
formation of loosely-bound compounds.
This effect explains the otherwise
surprising observation that a wide
variety of neutral
molecules such as
2
1and
2 even
1
hydrocarbons,
some of the
UDebye 2
(8)
2 6
40r r form stable hydrate
noble gas elements,

Dispersion or London Forces

(http://www.chem.ufl.edu/~itl/4411/lectures/lec_g.html)

Noble gas elements and completely nonpolar molecules such as H2 and N2 can be
condensed to liquids or solids.
There must be another source of
attraction between particles that does
not depend on the existence of

 A molecule is nonpolar the timeaveraged dipole moment is zero.

On a very short time scale, however, the
electron must be increasingly localized.
As a consequence, there is no guarantee
that the distribution of negative charge
around the center of an atom will be
perfectly symmetrical at every instant;
every atom therefore has a weak,
fluctuating dipole moment that is
continually disappearing and reappearing in
another direction.
Although these extremely short-lived
fluctuations quickly average out to zero,
they can still induce new dipoles in a

 Dispersion is applicable to all atoms or

molecules (unlike Keesom or Debye
interaction).
It is responsible for certain phenomena
in macro-scopic scale (adhesion,
surface tension, physical adsorption,
wetting, properties of gases and liquid,
structures of condensed
macromolecules,... ).
It is a long range force that can be
effective at large distance (>10 nm) to
interatomic spacings.
Dispersion is non-additive. The

Fritz London (1937) proposed a theory

based on quantum mechanics to explain
dispersion
3 12 1 I1I2
ULondon
(9)
2 6
2 40 r I1 I2

here I is the first ionization potential I = h

van der Waals Interaction

Many kinds of molecules possess
permanent dipole moments, so liquids
and solids composed of these species
will be held together by a combination
of dipole-dipole, dipole-induced dipole,
and dispersion forces.
These weaker forces (that is, those
other than coulombic attractions) are
known collectively as van der
Waals forces.
These are short-ranged and weak

 All atoms and molecules, even nonpolar and uncharged ones, exert
attractive forces on each other.
This is a result of the atomic
polarizability 0 of atoms.
The constant motion of electrons in
atoms results in the fact that at any
given instant in time, any atom actually
has a finite electric dipole moment.
Despite the quantum-mechanical
uncertainty of position, even particles
as light as electrons have to occupy
some region of space at a given time.

In general, the van der Waals forces arise

from three different contributions:
(1)orientation or Keesom interaction;
(2)induction or Debye interaction; and
(3)dispersion or London interaction

in general the total van der Waals energy is gi

UvdW UKeesom
UDebye ULondon

(10)

 The dispersion term is the most

important of the three contributions,
as it is always present, regardless
whether permanent dipoles take part in
the interaction or not.
Moreover, usually the dispersion term
is also the strongest, contributing
around 80 - 100% to the total van der
Waals interaction energy.
A notable exception to this is water,
where in fact the Keesom interaction
dominates (about 70% of the total

Summary

Intermolecular forces are responsible

most properties of all the phases:
1. Gas: Vapor pressure, critical point,
and boiling point
2. Liquid: viscosity, diffusion, and
surface tension.
3. Solid: melting and sublimation.

 The calculation of the potential

energy involves assumptions
concerning the nature of attraction
and repulsion between molecules.
Intermolecular interaction is the
result of both short- and longrange effects.
Electrostatic, induction, and
dispersion effects are examples of

 In these cases, the energy of

interaction is proportional to some
inverse power of intermolecular
separation. Electrostatic
interactions result from the static
charge distribution between
molecules.
The effect can be either attractive
or repulsive and it is exclusively
pairwise additive.
Induction effects are always

 The specification of intermolecular

potential, representing interaction
between molecules, is a critical step in
Molecular Dynamics simulations.
Generally, a two-body potential of the
form U(rij) is used, where rij is the
distance between the centers of
molecules i and j.
This form neglects multibody
interactions.
Once the potential is prescribed, the
intermolecular force is obtained from
Fij = -dU(rij)/drij.

ard-Sphere Potential
In this model, the molecules move freely
and do not interact with one another
except when they collide. The
intermolecular potential is given by
U r
r
U r 0

(11)

Here () is the diameter of the

molecule.
Thus the molecules exert force on one

termolecular potential for the hard-sphere mo

www.uic.edu/eng/ems/MEng/ChEME494/pdf/L8pt1.pdf

quare-Well Potential
The square-well potential is the simplest
inter-molecular potential that is capable
of representing the properties of liquids

U r
0

r
r
r

(12)

where is some multiple of the hardsphere diameter and is a measure of

the attractive interaction.
The square-well potential represents a
mathematically idealised model of

U(r
)

Square well potential model

Yukawa Potential
The square-well potential can be made
more realistic by changing the variation of
attractive interactions. There have been
many such variations of which the Yukawa
potential is an important example.
r

U r

r exp
1

(13)

where is an attractive term (depth of

potential well), is the hard-sphere
diameter and is an adjustable parameter.
The inverse power dependence of this
potential means that it can be applied to

ore Yukawa potential with various interaction r

(Naresh and Singh, 2000)

ennard-Jones Potential:
The Lennard-Jones potential (also referred
to as the L-J potential, 6-12 potential, or
12-6 potential) is a mathematically simple
model that approximates the interaction
between a pair of neutral atoms or
molecules. 12 6

U r 4
r

(14)

where is the depth of potential well, is

the hard-sphere diameter (the finite
distance at which the inter-particle
potential is zero), and r is the distance
between the particles.

Lennard-Jones potential

//what-when-how.com/molecular-biology/van-der-waals-interactions-molecular-bi

www.uic.edu/eng/ems/MEng/ChEME494/pdf/L8pt1.pdf

 The parameter is the zero energy

separation distance, and defines a
molecular length scale related to the
particle diameter, while is the
minimum energy and controls the
strength of the interaction.
As an example, = 0.41 nm, and /kB =
221K for xenon, where kB is the
Boltzmann's constant.
For a pure substance, equals the
particle diameter.
The parameter is also related to the

For simulations involving two fluids,

and are expressed using the LorentzBerthelot mixing rules (Allen and
Tildesley, 1984), as:
1
ij i j
(15)
2
ij i j

(16)

Intermolecular Force
The force between the two L-J molecules
is given by
dU
13 7
F
24 2
(17)
dr
r
r
By convention, repulsive (short-range)
forces are positive while attractive
(long-range) forces are negative. i.e.,
Repulsion
: F 0 for

r 21 6

Attraction
: F 0 for

r 21 6

(18)

Lennard-Jones intermolecular force

www.uic.edu/eng/ems/MEng/ChEME494/pdf/L8pt1.pdf