29 - CHAPTER 3 Intermolecular Forces and Potential Enegy Surfaces

CHAPTER -3
Intermolecular forces and potential energy surfaces
Ionic bonding is a type of chemical bonding that involves the electrostatic

attraction between oppositely charged ions, and is the primary interaction
occurring in ionic compounds.
Dipole-Dipole Interactions
Definition of a Dipole
Molecular dipoles occur due to the unequal sharing of electrons between atoms in a
molecule. Those atoms that are more electronegative pull the bonded electrons
closer to themselves. The buildup of electron density around an atom or discreet
region of a molecule can result in a molecular dipole in which one side of the
molecule possesses a partially negative charge and the other side a partially
positive charge. Molecules with dipoles that are not canceled by their molecular
geometry are said to be polar.
Dipole-Dipole interactions result when two dipolar molecules interact with each
other through space. When this occurs, the partially negative portion of one of the
polar molecules is attracted to the partially positive portion of the second polar
molecule. This type of interaction between molecules accounts for many physically
and biologically significant phenomena such as the elevated boiling point of water.
Vander Waals Interactions
Van der Waals interaction, named after Dutch scientist Johannes Diderik van
der Waals, is the sum of the attractive or repulsive forces between molecules (or
between parts of the same molecule) other than those due to covalent bonds, or
the electrostatic interaction of ions with one another, with neutral molecules, or
with charged molecules. The resulting Van der Waals forces can be attractive or
repulsive
Van der Waals forces are driven by induced electrical interactions between two or
more atoms or molecules that are very close to each other. Van der Waals
interaction is the weakest of all intermolecular attractions between molecules.
However, with a lot of Van der Waals forces interacting between two objects, the
interaction can be very strong.
 The main characteristics of van der Waals forces are:-

 They are weaker than normal covalent ionic bonds.
 Van der Waals forces are additive and cannot be saturated.
 They have no directional characteristic.
 They are all short - range forces and hence only interactions between nearest
need to be considered instead of all the particles. The greater is the attraction
if the molecules are closer due to Van der Waals forces.
 Van der Waals forces are independent of temperature except dipole - dipole
interactions.
The important aspects of Quantum Mechanics strongly suggest that the electrons
are constantly are moving in an atom, so dipoles are probable of occurring. A
dipole is defined as molecules or atoms with equal and opposite electrical charges
separated by a small distance.This is how instantaneous dipoles occur. When
groups of electrons move to one end of the atom, it creates a dipole.
It is probable to find the electrons in this state:
Potential Energy Surfaces
A potential energy surface (PES) describes the potential energy of a system,
especially a collection of atoms, in terms of certain parameters, normally the
positions of the atoms. The surface might define the energy as a function of one or
more coordinates; if there is only one coordinate, the surface is called a potential
energy curve or energy profile. It is helpful to use the analogy of a landscape: for a
system with two degrees of freedom (e.g. two bond lengths), the value of the
energy (analogy: the height of the land) is a function of two bond lengths (analogy:
the coordinates of the position on the ground). The Potential Energy Surface
represents the concepts that each geometry (both external and internal) of the
atoms of the molecules in a chemical reaction is associated with it a unique
potential energy. This creates a smooth energy “landscape” and chemistry can be
viewed from a topology perspective (of particles evolving over "valleys""and
passes").
Potential Energy Curves (1-D Potential Energy Surfaces)
The PES is the energy of a molecule as a function of the positions of its nuclei r
. This energy of a system of two atoms depends on the distance between them. At
large distances the energy is zero, meaning “no interaction”. At distances of
several atomic diameters attractive forces dominate, whereas at very close
approaches the force is repulsive, causing the energy to rise. The attractive and
repulsive effects are balanced at the minimum point in the curve. Plots that
illustrate this relationship are quite useful in defining certain properties of a
chemical bond.
Figure 2.6.1: A potential Energy Curve for a covalent bond.
The internuclear distance at which the potential energy minimum occurs defines
the bond length. This is more correctly known as the equilibrium bond length,
because thermal motion causes the two atoms to vibrate about this distance. In
general, the stronger the bond, the smaller will be the bond length.
Attractive forces operate between all atoms, but unless the potential energy
minimum is at least of the order of RT, the two atoms will not be able to withstand
the disruptive influence of thermal energy long enough to result in an identifiable
molecule. Thus we can say that a chemical bond exists between the two atoms in
H2. The weak attraction between argon atoms does not allow Ar2 to exist as a
molecule, but it does give rise to the van Der Waals force that holds argon atoms
together in its liquid and solid forms.
Potential, Kinetic, and Total Energy for a System .Potential energy and kinetic
energy Quantum theory tells us that an electron in an atom possesses kinetic
energy K
as well as potential energy V, so the total energy E is always the sum of the two:
E=V+K. The relation between them is surprisingly simple: K=–0.5V. This means
that when a chemical bond forms (an exothermic process with ΔE<0), the decrease
in potential energy is accompanied by an increase in the kinetic energy (embodied
in the momentum of the bonding electrons), but the magnitude of the latter change
is only half as much, so the change in potential energy always dominates. The
bond energy –ΔE has half the magnitude of the fall in potential energy.
Mathematical definition and computation
The geometry of a set of atoms can be described by a vector, r, whose elements

represent the atom positions. The vector r
could be the set of the Cartesian coordinates of the atoms, or could also be a set of
inter-atomic distances and angles. Given r, the energy as a function of the
positions, V(r), is the value of V(r) for all values of r of interest. Using the
landscape analogy from the introduction, V(r) gives the height on the "energy
landscape" so that the concept of a potential energy surface arises. An example is
the PES for water molecule (Figure 2.6.1) that show the energy minimum
correponding to optimized molecular structure for water- O-H bond length of
0.0958 nm and H-O-H bond angle of 104.5°
Figure 2.6.2 : PES for water molecule: Shows the energy minimum corresponding
to optimized molecular structure for water- O-H bond length of 0.0958nm and H-
O-H bond angle of 104.5°. Image used with permission of Wikipedia (Credit:
Aimnature).
The Dimensionality of a Potential Energy Surface
To define an atom’s location in 3-dimensional space requires three coordinates

(e.g., x
, y,and z or r, θ and phi
in Cartesian and Spherical coordinates) or degrees of freedom. However, a reaction

and hence the corresponding PESs do not depend of the absolute position of the
reaction, only the relative positions (internal degrees). Hence both translation and
rotation of the entire system can be removed (each with 3 degree of freedom,
assuming non-linear geometries). So the dimensionality of a PES is
3N−6(2.6.1)
where N is the number of atoms involves in the reaction, i.e., the number of atoms
in each reactants). The PES is a hypersurface with many degrees of freedom and
typically only a few are plotted at any one time for understanding. See Calculate
Number of Vibrational Modes to get a more details picture of how this applies to
calculating the number of vibrations in a molecule
To study a chemical reaction using the PES as a function of atomic positions, it is

necessary to calculate the energy for every atomic arrangement of interest.
Methods of calculating the energy of a particular atomic arrangement of atoms are
well described in the computational chemistry article, and the emphasis here will
be on finding approximations of (V(r) to yield fine-grained energy-position
information.
For very simple chemical systems or when simplifying approximations are made
about inter-atomic interactions, it is sometimes possible to use an analytically
derived expression for the energy as a function of the atomic positions. An
example is
H+H2→H2+H(2.6.2)
system as a function of the three H-H distances. For more complicated systems,
calculation of the energy of a particular arrangement of atoms is often too
computationally expensive for large scale representations of the surface to be
feasible.
Application of Potential Energy Surfaces

A PES is a conceptual tool for aiding the analysis of molecular geometry and
chemical reaction dynamics. Once the necessary points are evaluated on a PES, the
points can be classified according to the first and second derivatives of the energy
with respect to position, which respectively are the gradient and the curvature.
Stationary points (or points with a zero gradient) have physical meaning: energy
minima correspond to physically stable chemical species and saddle points
correspond to transition states, the highest energy point on the reaction coordinate
(which is the lowest energy pathway connecting a chemical reactant to a chemical
product). Three
 PES does not show kinetic energy, only potential energy.

 At T = 0 K (no KE), species will want to be at the lowest possible potential
energy, (i.e., at a minimum on the PES).
 Between any two minima (valley bottoms) the lowest energy path will pass
through a maximum at a saddle point.

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CHAPTER -3

Intermolecular forces and potential energy surfaces

Ionic bonding is a type of chemical bonding that involves the electrostatic

 The main characteristics of van der Waals forces are:-

Potential Energy Curves (1-D Potential Energy Surfaces)

Mathematical definition and computation

The geometry of a set of atoms can be described by a vector, r, whose elements

The Dimensionality of a Potential Energy Surface

To define an atom’s location in 3-dimensional space requires three coordinates

, y,and z or r, θ and phi

in Cartesian and Spherical coordinates) or degrees of freedom. However, a reaction

To study a chemical reaction using the PES as a function of atomic positions, it is

Application of Potential Energy Surfaces

 PES does not show kinetic energy, only potential energy.

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