Potential Energy Surface
Potential Energy Surface
Potential Energy Surface
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).
A potential energy surface (PES) represents the relationship between the energy of a
molecule and its geometry.
• 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.
Conformations
• In the eclipsed conformation, the C—H bonds on one carbon are directly aligned with the
C—H bonds on the adjacent carbon.
• In the staggered conformation, the C—H bonds on one carbon bisect the H—C—H bond
angle on the adjacent carbon.
Ethane
q2
R BC
q1
q
R BC
D
RC
RCD
RBC RBC
Variable(s) in PES
U(q1)
U(q1, q2) q1, q2, …∈ {Rn, qn} or {xn, yn, zn}
U(q1, q2, q3)
U(q1, q2, q3, … …qn)
More ”Realistic” PES
a
0
PES for proteins
Characterizing Potential Energy Surface
The most interesting points on PES’s are the stationary points, where the gradients
with respect to all internal coordinates are zero.
2. Transition states: saddle points which are minima in all dimensions but one; a
maximum in that dimension.
Local minimum
Ts
Energy
Ts
R
Intermediate I
Reaction coordination
Global minimum
Reactants For a minimum Stationary point