A new theoretical approach in photochemistry. Minimization of excited state–ground state surface separation by selected molecular deformation. Vibrational dissipation of local contributions to excitation energies

Abstract

A new method is described for prediction of photochemical reactions by determining which molecular motions convert electronic into vibrational energy and thus minimize excited state–ground state energy separation; the method works generally on a large variety of photochemical reactions, and on the more limited set subject to orbital control, it affords predictions consistent with the Woodward–Hoffmann and Zimmerman Möbius–Hückel methods.