Unimolecular dissociation of HOCl: unexpectedly broad distribution of rate constants

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 energy surface. At threshold, the state-resolved rate constants are scattered over seven orders of magnitude, which is significantly broader than the distribution predicted by random matrix theory. This remarkable state specificity is the fingerprint of the regular dynamics of HOCl even at high energies.