Journal of Chemical Physics, Vol.107, No.9, 3542-3549, 1997
A theory for nonisothermal unimolecular reaction rates
A simple expression is derived for the survival probability of a reactive chemical species which is initially prepared at a temperature which differs from its surrounding. The competition between relaxation of reactants back to the external equilibrium and the possibility of reaction may prevent the usual single exponential kinetics for the survival probability. The theory is accurate for activated reactions with moderate (V double dagger/k(B)T greater than or equal to 3) to high reduced barrier heights. It is especially relevant for multidimensional systems where the characteristic energy at which a molecule dissociates is greater than the barrier height. (C) 1997 American Institute of Physics.