Molecular dynamics in low-spin excited states

摘要

A Kohn-Sham-like formalism is introduced for the treatment of excited singlet states. Motivated by ideas of Ziegler's sum method and of restricted open-shell Hartree-Fock theory, a self-consistent scheme is developed that allows the efficient. and accurate calculation of excited state geometries. Vertical as well as adiabatic excitation energies for the n-->pi* transitions of several small molecules are obtained with reasonable accuracy. As is demonstrated for the cis-trans isomerization of formaldimine, our scheme is suited to perform molecular dynamics in the excited singlet state. This represents a first step towards the simulation of photochemical reactions of large systems. (C) 1998 American Institute of Physics. [S0021-9606(98)0421O-X]. [References: 95]