Intermolecular Forces and Potential

Energy Surfaces
Dr. Saurav Prasad
 States of Matter
▪ The fundamental
difference between
states of matter is the
strength of the
intermolecular forces of
attraction.
▪ Stronger forces bring
molecules closer
together.
▪ Solids and liquids are
referred to as the
condensed phases.
Differences in the States of
Matter
Which State of Matter?
•The answer to this
question largely relies
on the
balance between the
kinetic energies of the
particles.
interparticle energies of
attraction.
intER vs. intRA molecular
forces
• Intramolecular forces are the forces within a molecule or
ionic compound

Example: Individual therapy

NaCl Ionic bond between atom of Na and atom of Cl

• Intermolecular forces are the forces between molecules or

ions and molecules
Example: couples therapy
Solid liquid gas

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 Intermolecular Forces

• The attractions between molecules are not nearly as strong

as the intramolecular attractions (bonds) that hold
compounds together.
• Many physical properties reflect intermolecular forces, like
boiling points, melting points, viscosity, surface tension,
and capillary action.
Types of Intermolecular Force
•Weakest to strongest forces:
dispersion forces (or London dispersion
forces)
dipole–dipole forces
hydrogen bonding (a special
dipole–dipole force)
ion–dipole forces
oNote: The first two types are also referred
to collectively as van der Waals forces.
 Dispersion Forces
• The figure below shows how a nonpolar particle
(in this case a helium atom) can be temporarily polarized
to allow dispersion force to form.
• The tendency of an electron cloud to distort is
called its polarizability.
 Factors Which Affect Amount of
Dispersion Force in a Molecule
• number of electrons in an atom
(more electrons, more dispersion
force)
• size of atom or
molecule/molecular weight
• shape of molecules with similar
masses (more compact, less
dispersion force)
Dipole–Dipole Interactions
• Polar molecules have a more positive and a more
negative end–a dipole (two poles, δ+ and δ−).
• The oppositely charged ends attract each other.
Dipole–Dipole Interactions

For molecules of approximately equal mass and size, the

more polar the molecule, the higher its boiling point.
Question
1. Calculate the dipole moment of a water
model having following characteristics: rOH =
0.97 Å, HOH angle = 104.5o, qO = -0.6e and
qH = +0.3e.
Which Have a Greater Effect:
Dipole–Dipole Interactions or
Dispersion Forces?
• If two molecules are of comparable size and shape,
dipole–dipole interactions will likely be the
dominating force.
• If one molecule is much larger than another,
dispersion forces will likely determine its physical
properties.
 What Does This Graph Show Us?

• In a group, the period 3/4/5

elements have higher boiling
points as the group member
gets larger.
• What happens with the
period 2 elements? For group
4A, the trend is continued.
What about for the other
groups?
 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.
• A hydrogen bond is an attraction
between a hydrogen atom
attached to a highly
electronegative atom and a nearby
small electronegative atom in
another molecule or chemical
group.
 What Forms Hydrogen Bonds?
• Hydrogen bonding arises in part from the high
electronegativity of nitrogen, oxygen, and fluorine.
• These atoms interact with a nearly bare nucleus (which
contains one proton).
 Ion–Dipole Interactions
• Ion–dipole interactions are found in solutions of ions.
• The strength of these forces is what makes it possible for
ionic substances to dissolve in polar solvents.
Summarizing Intermolecular Forces
Liquid Properties Affected by
Intermolecular Forces
• boiling point (previously discussed) and melting
point
• viscosity
• surface tension
• capillary action
 Viscosity
• Resistance of a liquid to flow is called viscosity.
• It is related to the ease with which molecules can move past each
other.
• Viscosity increases with stronger intermolecular forces and
decreases with higher temperature.
Surface Tension

• Water acts as if it has a

“skin” on it due to extra
inward forces on its
surface. Those forces
are called the surface
tension.
Cohesion and Adhesion
• Intermolecular forces that bind similar molecules to
one another are called cohesive forces.
• Intermolecular forces that bind a substance to a
surface are called adhesive forces.
• These forces are important in capillary action.
 Capillary Action
• The rise of liquids up narrow
tubes is called capillary
action.
• Adhesive forces attract
the liquid to the wall of
the tube.
• Cohesive forces attract
the liquid to itself.
• Water has stronger adhesive
forces with glass; mercury has
stronger cohesive forces with
itself.
CONCEPT CHECK!

Which molecule is capable of forming stronger

intermolecular forces?

N2 H2O

Explain.

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CONCEPT CHECK!

Draw two Lewis structures for the formula C2H6O

and compare the boiling points of the two
molecules.

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CONCEPT CHECK!

Which gas would behave more ideally at the same

conditions of P and T?

CO or N2

Why?

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CONCEPT CHECK!

What type(s) of intermolecular forces exist between the

following pairs?

(a) HBr and H2S

(b) Cl2 and CBr4

(c) I2 and

(d) NH3 and C6H6

 CONCEPT CHECK!
Which of the following can form hydrogen bonds with water?

CH3OCH3

CH4

F2

HCOOH

Na+
 Hydrophobic Effect

The hydrophobic effect is an entropically-driven association of hydrophobic

molecules that is a direct consequence of the polar nature of water and it
propensity for hydrogen bonding.
Reading Materials and Simulation
Link

❑ [Link]
1c2-4aac-9d4d-9e110fb97734/items/lx-pb:d434428e-91c2-4aac-9d4d
-9e110fb97734:video:e8f4301c

❑ [Link]
4/intermolecular-forces

❑ [Link]
er/intermolecular-forces/
 Potential Energy Surface
• Atoms in a molecule are held together by chemical bonds. When the
atom is distorted, the bonds are stretched or compressed, in which
increases the potential energy of its system.

• As the new geometry is formed, the molecule stays stationary. Therefore,

the energy of the system is not caused by the kinetic energy, but
depending on the position of the atoms (potential).

• Energy of a molecule is a function of the position of the nuclei. When

nuclei moves, electron readjusts quickly. The relationship between this
molecular energy and molecular geometry (position) is mapped out with
potential energy surface.
 Potential Energy Surface

• A potential energy surface is a mathematical function that

gives the energy of a molecule as a function of its geometry.

• Does not change if it translated or rotated in space

• Depends on a molecule’s internal coordinates

 Potential Energy Surface
A potential energy surface (PES) represents the relationship between the energy of
a molecule and its geometry.

The y-axis is energy of the

molecule, which relates how stable
two molecules or two
conformations of the same
molecule are in relation to one
another. The more negative a
molecule's energy, or the lower on
the y-axis, the more stable it is.
 Potential Energy Surface
Fully specifying the location of a diatomic molecule, AB, would require specifying
six numbers, the x, y, and z coordinates of each of its atoms.

Potential energy (PE) of the molecule as a function of the distance between the two
atoms dAB.
Potential Energy Surface
 This PES shows the energy differences between the
Potential two conformations of ethane. The eclipsed
Energy conformation with the hydrogen atoms overlapping
one another is about 2.6 kcal/mol higher in energy
Surface than the staggered conformation.
 Force-field
• A Force field is a computational method that is used to estimate the forces
between atoms within molecules and also between molecules.
• It refers to the functional form and parameter sets used to calculate
the potential energy of a system of atoms or coarse-grained particles
in molecular mechanics, molecular dynamics, or Monte Carlo simulations.
• The parameters for a chosen energy function may be derived from
experiments in physics and chemistry, calculations in quantum mechanics,
or both.
• Force fields are interatomic potentials and utilize the same concept as force
fields in classical physics, with the difference that the force field
parameters in chemistry describe the energy landscape, from which the
acting forces on every particle are derived as a gradient of the potential
energy with respect to the particle coordinates.
Interactions in molecules
 What is the Potential?
A single atom will be affected by the potential energy
functions of every atom in the system:

• Bonded Neighbors
• Non-Bonded Atoms (either other atoms in the same
molecule, or atoms from different molecules)
 Non-Bonded Atoms
There are two potential functions between non-bonded atoms that we need to
know:
• van der Waals Potential
• Electrostatic Potential

One of the most widely used functions for the ▪ Opposite Charges Attract
van der Waals potential is the Lennard-Jones. ▪ Like Charges Repel
Constants A and C depend on the atom types
and are derived from experimental data.
 Bonded Atoms
There are three types of interaction between bonded atoms:
• Stretching along the bond

• Bending between bonds

• Rotating around bonds (Torsions)

 The Electrostatic Potential
• Opposite Charges Attract
• Like Charges Repel
• The force of the attraction is inversely proportional to
the square of the distance
The van der Waals Potential
• Atoms with no net electrostatic charge will still tend
to attract each other at short distances, as long as
they don’t get too close.
• Once the atoms are close enough to have
overlapping electron clouds, they will repel each
other with astounding force
Bonded Atoms
There are three types of
interaction between
bonded atoms:

• Stretching along the bond

• Bending between bonds
• Rotating around bonds
 Bond Length Potentials
Both the spring constant and the
ideal bond length are dependent on
the atoms involved.

This is the approximation to the energy of a

bond as a function of displacement from the
ideal bond length, b0. The force
constant, Kb, determines the strength of the
bond. Both ideal bond lengths b0 and force
constants Kb are specific for each pair of bound
atoms, i.e. depend on chemical type of
atoms-constituents.
 Bond Angle Potentials
The spring constant and the ideal
angle are also dependent on the
chemical type of the atoms.

It is the alteration of bond angles theta from

ideal values q0 , which is also represented by
a harmonic potential.

Values of q0 and Kq depend on chemical type

of atoms constituting the angle.
 Torsional Potentials
Described by a dihedral angle
and coefficient of symmetry
(n=1,2,3), around the middle
bond.
 Pair-wise additivity
• An approximation introduced to decrease the computational demand is
the pair-wise additive approximation, i.e., interaction energy between
one atom and the rest of the system is calculated as a sum of pair-wise
(on atom to one atom) interactions, or as if the pair of atoms do not see
the other atoms in the system.
• The simultaneous interaction between three or more atoms is not
calculated, so certain polarization effects are not explicitly included in
the force field.
• This can lead to subtle differences between calculated and
experimental results, for example, in the calculation of experimentally
observable pK shifts of ionizable amino acid residue side chains
induced by electrostatic field of the whole protein .
Thank you