Direct semiclassical simulation of photochemical processes with semiempirical wave functions

Abstract

We describe a new method for the simulation of excited state dynamics, based on classical trajectories and surface hopping, with direct semiempirical calculation of the electronic wave functions and potential energy surfaces (DTSH method). Semiempirical self-consistent-field molecular orbitals (SCF MO’s) are computed with geometry-dependent occupation numbers, in order to ensure correct homolytic dissociation, fragment orbital degeneracy, and partial optimization of the lowest virtuals. Electronic wave functions are of the MO active space configuration interaction (CI) type, for which analytic energy gradients have been implemented. The time-dependent electronic wave function is propagated by means of a local diabatization algorithm which is inherently stable also in the case of surface crossings. The method is tested for the problem of excited ethylene nonadiabatic dynamics, and the results are compared with recent quantum mechanical calculations.