EXPLORING POTENTIAL-ENERGY SURFACES WITH TRANSITION-STATE CALCULATIONS

Means are presented for using stationary points in two ways. One, for well-understood potentials, elucidates relations between the form of the surface and the dynamics that it supports, including the determination of the effective molecular symmetry group. The other, for potentials of uncertain quality, provides a test for unphysical characteristics and suggests how the surface might be improved if it is found to be unsatisfactory in some respect. Our approach involves comparison of transition state calculations using the slowest slide and Cerjan-Miller algorithms for two example systems: the Lennard-Jones Ar7 cluster and the Handy-Carter many-body-expansion potential for the ground state of formaldehyde. © 1990 American Institute of Physics.