COMPUTATIONAL CHEMISTRY
SEMESTER II [Link] CHEMISTRY
M.G UNIVERSITY KOTTAYAM
Aby Jimson
Dept of Chemistry
St. Stephen’s College
Uzhavoor, Kottaym
TOPICS
Conformational Search & Geometry Optimisation
Potential Energy Surface
Global Minimum & Local Minima
Saddle Point
ENERGY & GEOMETRY
Each Structure with a given geometry has an associated energy
This energy changes with geometry
The most stable geometry is the one which yields minimum energy
GEOMETRY OPTIMISATION
• Its objective is to find an atomic arrangement (geometry) which makes the molecule most stable.
ie Lowest energy.
• Here we check for the lowest possible energy of a molecule.
• And this is achieved by creating a “Potential Energy Surface”
POTENTIAL ENERGY SURFACE
• PES is a mathematical relationship between different molecular geometries and their corresponding
energies.
• The values are displayed on a 3 D graph
• Where 3 dimensions represent
• Bond Angle
• Bond Length
• Hartree- Fock Energy
DIATOMIC MOLECULE
• Consider Hydrogen Molecule
• Simplest system
• We only need to consider the bond length.()
• Energy of the molecule varies as we shorten or lengthen the bond
• We need two axes to represent the energy (E and )
• Therefore we get a 1 D PES on a 2 D graph
1 D PES REPRESENTED IN A 2 D GRAPH
THE GRAPH
• 1 D PES represented on a 2 D graph
• 1 D PES since only one parameter( bond length varies)
WATER MOLECULE
• 3 atom system
• Both hydrogens are identical
• Energy depends on O-H bond () length and H-O-H (Ø) bond angle
• we need 3 axes to represent this molecule (E, , Ø)
• Therefore we get a 2 D PES on a 3D graph
HOF MOLECULE
• Three geometric parameters, O-H & O-F bond length and H-O-F bond angle
• So we need 4 axes to represent (E, , , Ø)
• HOF PES is a 3 D surface in 4 D space or it is a Hyper Surface
• We define equation as the PES for HOF
• Note that here f is a function that describes how E varies with theses parameters and thus treat
hyper structure mathematically
STATIONARY POINTS
• A stationary point on a PES is a point at which the surface is flat, parallel to the horizontal line
corresponding to one geometric parameter or to the plane corresponding to two parameters or to
a hyperplane corresponding to more parameters.
• A ball placed on a stationary point will remain balanced. At any other point on PES the ball will
roll down to lower potential. Stationary points help us to visualise the relationship between
potential energy and molecular geometry.
OZONE- CYCLIC OZONE
Consider the hypothetical reaction Ozone forming cyclic ozone via a transition state
The PES here must be plotted with E against 2 geometric parameters, O-O bond length and O-O-
O bond angle (considering both O-O bond lengths are the same)
EXPLORING THE GRAPH
Stationary points - corresponds to actual molecules with finite life time like ozone, cyclic ozone
etc are minima or energy minima each occupying the lowest energy point in its region of the PES
and any small change in geometry increases the energy.
ozone is a “global minimum” Since it is the lowest point on the PES
Cyclic Ozone is a “relative minimum”, a minimum compared to only nearby points
The lowest energy pathway linking two minima is called “Intrinsic reaction coordinate”(IRC). It
is the path followed by the molecule in going from one minimum to another.
Note that a molecule with excess energy may stray out of IRC.
SADDLE POINT
T.S is the maximum point on IRC. But it along all other directions (except IRC) is a minimum.
This is the characteristic of a saddle shaped surface and such a transition state is called a saddle
point.
A point on a PES which is a maximum in one direction and minimum in all other directions is
called a saddle point. They represent transition structures connecting two equilibrium states.
Note
• Both Minima and saddle points are stationary points. Minima is a minimum in all directions but
saddle point is a maximum along IRC and minimum along all other directions.
