Crystal Binding

(Bonding) Part VI
More on Van der Waals
& Hydrogen Bonding
 Van Der Waals Bonding
• A WEAK dipole-dipole interaction is
the origin of the Van der Waals bond,
which is therefore characterized by a
LOW cohesive energy, & so LOW
melting temperatures

+ - + -
 + - + -

• Also, spontaneous dipole formation in

one atom may induce an equal &
opposite dipole in another atom nearby,
causing attraction between them
through the dipole dipole
interaction.
•Another type of van der Waals
bonding is observed for certain\
POLAR molecules that have a
PERMANENT dipole moment

+ - + -
 Van Der Waals Bonding
• Although atoms are electrically NEUTRAL,
the electrons within them are in a constant
state of motion, and so may MOMENTARILY
form small electric DIPOLES. The direction
& magnitude of these dipoles are constantly
fluctuating, but may INDUCE similarly
fluctuating dipoles in other atoms.

+e -e

+ -
• The Van der Waals potential energy can be
APPROXIMATED as
2nd term = classical
A B dipole-dipole interaction  r-6.
E (r )  n  m 1st term = repulsion for small r.
r r Typically people use
A & B are empirical n = 12, m = 6
parameters, as is n
At equilibrium , we have
1
dE  nA  nm 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 )  n  m
r r
dE nA mB
 0   n 1  m 1
dr r  ro r r
nA mB mn mB
n 1
 m 1  r 
r r nA

1
 nA  nm B m 
ro    & E (ro )  m  n  1
 mB  ro  
 Lennard-Jones Potential
• Attraction due to instantaneous dipole of
molecules
• Short range force
• Use cut-off radius to reduce computations
 &  are empirical parameters chosen
by fits to data.

  12
  
6

U LJ  4      
 r   r  
 Lennard-Jones Potential of Argon gas
300

250

200

  12    6  150
U LJ  4      

v(r)/kb (K)
 r   r  
100

50

0
0.3 0.5 0.7 0.9 1.1 1.3 1.5
-50

-100

-150
r (nm )
 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: Noble Gas Atoms
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)/ε
Dipole-dipole (including H-bonding)
Induced dipole
London dispersion attraction

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

   12   6 
E  4       
Two atoms:  R   R   R
R

ε

repulsion dispersion (van der Waals)

Multiple atoms -    12    6 
a E  4       
assume pairwise  
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
 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.
 Intermolecular Potentials
Dense Gases, Liquids and Solids
Gases
• • Electric dipole ~ r -3
No long range interactions
• • 2 dipoles ~ r
Interact via elastic collisions
-6

•
“Hard Sphere” Potential Repulsive nuclear forces ~ r -12

• Total Potential = (Attractive) + (Repulsive)

“Lennard-Jones 6-12 Potential”

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