Unimolecular dissociation of HOCl: unexpectedly broad distribution of rateconstants

The dissociation of HOCl in its electronic ground state is investigated by means of quantum dynamics calculations (filter diagonalization and harmonic inversion of the autocorrelation function) and an ab initio potential ener gy surface. At threshold, the state-resolved rate constants are scattered o ver seven orders of magnitude, which is significantly broader than the dist ribution predicted by random matrix theory. This remarkable state specifici ty is the fingerprint of the regular dynamics of HOCl even at high energies . (C) 1999 Elsevier Science B.V. All rights reserved.