Crystal Binding

(Bonding) Continued
More on Van der Waals
& Hydrogen Bonding
 Van Der Waals Bonding
This WEAK dipole interaction is the origin of the van der
Waals bond, which is therefore characterized by a LOW
cohesive energy, and so LOW melting temperatures

+ - + -
SPONTANEOUS DIPOLE FORMATION IN ONE ATOM
MAY INDUCE AN EQUAL AND OPPOSITE DIPOLE IN
ANOTHER ATOM NEARBY SO CAUSING ATTRACTION
THIS IS THE VAN DER WAALS BOND
Another type of van der Waals bonding is observed for
certain POLAR molecules, that have a PERMANENT
dipole moment
 Van Der Waals Bonding
Although IONIZED atoms are electrically NEUTRAL, electrons
within them are in a CONSTANT state of motion, and so may
MOMENTARILY form small charge DIPOLES
DIPOLE
+e -e
FORMS

+ -
A CHARGE DIPOLE MAY SPONTANEOUSLY
A DIPOLE CONSISTS OF EQUAL AND
FORM IN A NEUTRAL ATOM DUE TO THE MOTION
OPPOSITE CHARGES SEPARATED BY
OF ELECTRONS AROUND THE NUCLEUS
SOME DISTANCE

The direction and magnitude of this dipole

CONSTANTLY fluctuates, but may INDUCE similarly
fluctuating dipoles in other atoms
 Van Der Waals Bonding
Mathematically this potential energy variation can be
APPROXIMATED as typical values are
A B
E (r ) n m n = 12, m = 6
r r
The CONSTANTS A and n are associated with REPULSIVE
forces. The constants B and m are associated with
ATTRACTIVE forces. At EQUILIBRIUM these forces
BALANCE and we may write n1m
dE nA B m
0 ro & E ( ro ) m 1
dr r ro mB ro n

ro and E(ro) are the equilibrium SEPARATION and ENERGY

For a stable bond to form E(ro) must be NEGATIVE thus m < n
Van Der Waals Bonding
A B
E (r )
rn rm

dE nA mB
0 n 1 m 1
dr r ro r r
nA mB mn mB
r
r n 1 r m 1 nA

1
nA nm B m
ro & E (ro ) m
1
mB ro n
 Intermolecular Forces
The origin of intermolecular forces
The classification of intermolecular forces
Van der Waals force
Hydrogen bonding
Explore an example in depth to show the
significance of existence of intermolecular forces.
 The Origin of Intermolecular Forces
It is weak electrostatic force of attraction
that exist an area of negative charge on one
molecule
and an area of positive charge on a second
molecule.
What causes intermolecular forces?
Molecules are made up of charged
particles: nuclei and electrons. When one
molecule approaches another, there is a
multitude of interactions between the
particles in the two molecules. Each
electron in one molecule is subject to
forces from all the electrons and the nuclei
in the other molecule.
 Intermolecular force is weak compared to covalent
bond. It is relatively weak interactions that occur
between molecules.
There are 2 types of intermolecular forces (both of
them are electrostatic attraction between dipoles
formed by uncharged molecules.)
1. Van der Waals' force
2. Hydrogen bonding
Van der waals force is formed by dipoles. There
are 3 types of dipoles:
1. Permanent dipoles
2. Instantaneous dipoles
3. Induced dipoles
 Permanent Dipole
These molecules have a permanent separation of positive and negative
charge.

A simple example is HCl

+ -

The pair of electrons in the covalent bond between hydroge and chlorine is
unequally shared due to the difference in electronegativity between hydrogen and
chlorine. Chlorine has a greater electronegativity compared to hydrogen and hence
Chlorine tends to attract the bonded electron pair to itself. chlorine becomes slightly
negatively charged (-), hydroge atom has a partial positive charged (+) .The
unsymmetrical distributed charge on the HCl molecule produces a permanent
dipole.
 Instantaneous Dipole
Instantaneous dipole is due to the fluctuation of
electron clouds on non-polar molecules, positive and
negative charges exist temporarily.

Induced Dipole
Induced dipole exists when a permanent dipole or
instantaneous dipole comes close to a non-polar
molecule, the non-polar molecule will be induced to
form a dipole temporarily.
Classification diagram of intermolecular forces
 Dipole-Dipole Interactions
Dipole-dipole interactions exist between molecules which are permanent
dipole. They tend to orientate themselves that the attractive forces between
molecules are maximized while repulsive forces are minimized.
In the illustration :
the H end of HCl is permanently slightly positive charge. The Cl end of
HCl has a permanent slight negative charge, the "H" in one molecule is
attracted to the "Cl" in a neighbor.
 Instantaneous Dipole-Induced Dipole Interactions
Also known as London forces or Dispersion Forces
Instantaneous dipole-induced dipole Interactions exist in non-polar
molecules. These forces result from temporary charge imbalances. The
temporary charges exist because the electrons in a molecule or ion move
randomly in the structure. The nucleus of one atom attracts electrons form
the neighboring atom. At the same time, the electrons in one particle repel
the electrons in the neighbor and create a short lived charge imbalance.
These temporary charges in one molecule or atom attract opposite charges
in nearby molecules or atoms. A local slight positive charge + in one
molecule will be attracted to a temporary slight - negative charge in a
neighboring molecule.
Note: dispersion forces operate in all molecules whether they are polar or non-polar.
 Dipole-Induced Dipole Interactions
Also known as induction force.
When a polar molecule approaches a nonpolar molecule, the
permanent dipole on the polar molecule can distort the electron
cloud of the nonpolar molecule, forming an induced dipole.
 Van der Waals Radius & Covalent Radius
Van der Waals radius is one half
of the distance between the
nuclei of two atoms in adjacent
molecules.
Covalent radius is one half of
the distance between two atoms
in the same molecules.
Van der Waals radius of a non-
metal is always larger than the
corresponding covalent radius
because the covalent radius
because covalent bond is much
stronger than van der Waals
forces.
4) Van der Waals Bonds
Weakest bond
Usually between neutral molecules (even large
ones like graphite sheets)
Aided by polar or partial polar covalent bonds.
Even stable A-A bonds like O2 or Cl2 will get slightly
polar at low T & condense to liquid & ordered solid
as vibration slows & polarity
Weakness of the bond is apparent in graphite cleavage
 Van der Waals Bonding

created by weak bonding of oppositely dipolarized

electron clouds
commonly occurs around covalently bonded
elements
produces solids that are soft, very poor conductors,
have low melting points, low symmetry crystals
 Hydrogen Bonding
H+
Electrostatic bonding
between an H+ ion
with an anion or Close packing of Anions
anionic complex or polarized molecules
with a polarized
molecules
Weaker than ionic or
covalent; stronger than
polarized H2O
Van der Waals Ice
molecule
 Intermolecular Forces

These intermolecular forces as a group are referred

to as van der Waals forces.
 van der Waals Forces
Dipole-dipole interactions
Hydrogen bonding
London dispersion forces
 Ion-Dipole Interactions
A fourth type of force, ion-dipole interactions are
an important force in solutions of ions.
The strength of these forces are what make it
possible for ionic substances to dissolve in polar
solvents.
Dipole-Dipole Interactions
Molecules that have
permanent dipoles are
attracted to each other.
The positive end of one is
attracted to the negative
end of the other and vice-
versa.
These forces are only
important when the
molecules are close to
each other.
 Hydrogen Bonding

The dipole-dipole interactions

experienced when H is bonded
to N, O, or F are unusually
strong.
We call these interactions
hydrogen bonds.
 Hydrogen Bonding
Hydrogen bonding
arises in part from the
high electronegativity
of nitrogen, oxygen,
and fluorine.

Also, when hydrogen is bonded to one of

those very electronegative elements, the
hydrogen nucleus is exposed.
 Hydrogen Bonding
Hydrogen bond is a electrostatic force of attraction existing
between polar hydrogen(+) and electronegative atom(-) of
dipoles.
The hydrogen bond is weaker than the covalent bond, but
relatively strong compared to van der Waals force.
Hydrogen bonding is a unique type of intermolecular
molecular attraction. There are two requirements.
1. The first is a covalent bond between a H atom and either
F, O, or N (These are the three most electronegative
elements.)
2. The second is an interaction of the H atom in this kind of
polar bond with a lone pair of electrons on a nearby atom
of F, O, or N.
Hydrogen Bonding in an Ice Crystal

Ice has a lower

density than water
as ice has an open
structure. In ice,
each molecule is
tetrahedral bonded
to other molecules
by hydrogen bond.
 Hydrogen Bond in Water
Many other unique properties of water
are due to the hydrogen bonds. For
example, ice floats because hydrogen
bonds hold water molecules further
apart in a solid than in a liquid, where
there is one less hydrogen bond per
molecule. The unique physical
properties, including a high heat of
vaporization, strong surface tension,
high specific heat, and nearly
universal solvent properties of water
are also due to hydrogen bonding.
Hydrogen Bonding in DNA

Hydrogen bonds play an

important role in the base-
pairing duplication of DNA
(A-T,C-G). Matching of the
bases produces an accurate
duplicate of the original
DNA chain.
 Lennard-Jones Potential
Attraction due to instantaneous dipole of
molecules
Pair-wise non-bonded interactions O(N2)
Short range force
Use cut-off radius to reduce computations
Reduced complexity close to O(N)
 Lennard-Jones Potential of Argon gas

12

6

U LJ 4
r r
 Lennard Jones potentials
The Lennard-Jones potential
12

6

u r 4
LJ

r r

The truncated Lennard-Jones potential

u LJ r r rc
u r
0 r rc
The truncated and shifted Lennard-Jones potential
u LJ r u LJ rc r rc
u r
0 r rc
Lennard-Jones Potential
Some Lennard-Jones potential examples of application are
listed in the Table. Even this crude interaction model has
extensive applications. This model can explain many
properties of gases, solids and liquids quite well.
Minimum interaction energy and its distance
r0(A) (J)

He 2.2 1 10 -22

H2 2.7 4

Ar 3.2 15

N2 3.7 13

CO2 4.5 40
The Lennard-Jones Potential
12

6

u r 4
r r

The short range 1/r12 The long range

repulsive term 1/r6 attractive term

Contributions:
u(r)/
Dipole-dipole (including H-bonding)
Induced dipole
London dispersion attraction

r/
0 1 2 3
 Example Lennard-Jones (LJ) clusters E
21/6

12

6

E 4
Two atoms: R R R

R

repulsion dispersion (van der Waals)

Multiple atoms - 12

6

a
assume pairwise E 4

i j R ij
R
1 2 3 ij
additive:

b Isomers
1 3 2 different minima on potential energy surface
number of isomers grows exponentially
with # of atoms
c a and b permutation-inversion isomers
Ea = Eb Ec
 Intermolecular Potentials
Dense Gases, Liquids and Solids
Gases
Electric dipole ~ r -3
No long range interactions
2 dipoles
Interact via elastic collisions ~ r -6

Repulsive nuclear forces ~ r -12

Hard Sphere Potential
Total Potential = (Attractive) + (Repulsive)
Lennard-Jones 6-12 Potential

Carey, V.P., Statistical Thermodynamics and Microscale Thermophysics, New York: Cambridge University Press, 1999.