The concept of potential energy surface was very important in the development of TST. The foundation of this concept was laid by René Marcelin in 1913. He theorized that the progress of a chemical reaction could be described as a point in a potential energy surface with coordinates in atomic momenta and distances.
In 1931, Henry Eyring and Michael Polanyi constructed a potential energy surface for the reaction below. This surface is a three-dimensional diagram based on quantum-mechanical principles as well as experimental data on vibrational frequencies and energies of dissociation.
H + H → H + H
A year after the Eyring and Polanyi construction, Hans Pelzer and Eugene Wigner made an important contribution by following the progress of a reaction on a potential energy surface. The importance of this work was that it was the first time that the concept of col or saddle point in the potential energy surface was discussed. They concluded that the rate of a reaction is determined by the motion of the system through that col.
It has been typically assumed that the rate-limiting or lowest saddle point is located on the same energy surface as the initial ground state. However, it was recently found that this could be incorrect for processes occurring in semiconductors and insulators, where an initial excited state could go through a saddle point lower than the one on the surface of the initial ground state.