Rigidity factors in unimolecular reactions

Abstract

AbstractUnimolecular reactions with loose activated complexes, i.e. simple bond fission and the reverse bond formation processes, are conveniently characterized by phase space theory (PSD, which accounts for the maximum attraction potential between the fragments, and by additional rigidity factors which are the result of the anisotropy of the potential. This article summarizes recent calculations of specific rigidity factors frigid (E, J) and of thermal rigidity factors frigid (T) for a series of different potentials such as, e.g., ion‐dipole, dipole‐dipole, or standard valence potentials. The calculations have been made by rigorous statistical adiabatic channel (SACM) in combination with classical trajectory (CT) calculations.