Time-dependent wave packet study on trans-cis isomerization of HONO.

Abstract

Using a full six-dimensional ab initio potential energy surface and nuclear motion Hamiltonian, time-dependent computations were performed for the cis-trans isomerization of HONO. The multiconfiguration time-dependent Hartree method was used to propagate the six-dimensional wave packets. The initial excitations were chosen to be excitations of the local stretch modes and the HON local bend mode. The energy redistribution within 2 to 5 ps in the energy region of the OH stretching modes in both isomers was analyzed. The Fourier transformed frequency domain spectra were attributed to the eigenstates calculated previously by the time-independent variational approach. The results are also compared with classical trajectory computations of Thomson et al. on empirical surfaces. In agreement with matrix experiments, the cis-->trans isomerization was found to be much faster than the opposite interconversion. The intramolecular dynamics were found to be very complex involving numerous weakly excited delocalized eigenstates and anharmonic resonances. Particularly in the cis-isomer, the excitation of the HON bending local mode leads to fast energy redistribution in cis-trans delocalized modes. Neither the excitation of the OH stretching local mode in the cis nor in the trans form produces a fast isomerization, in agreement with the strongly localized characters of the corresponding eigenstates calculated variationally by Richter et al. and the gas phase spectra of HONO.