Spin-orbit induced predissociation dynamics of HCl+ and HBr+ ions:: temporal and spectral representations

The spin-orbit induced predissociation dynamics of HCl+ and HBr+ ions have been investigated by numerical solution of four coupled time-dependent Schrodinger equations based on ab initio potential energy data. For HCl+ exponential decay dominates for all vibrational levels in the electronic excited (2)Sigma(+) state. For HBr+ pronounced nonexponential decay occurs due to significant multichannel competition. The comparison of temporal and spectral representations of the dynamics reveals that the derivation of dynamic information from experimental frequency domain spectra may be difficult in the case of multichannel competition. (C) 2000 Elsevier Science B.V.