Photochemical processes, nonadiabatic quantum

With respect to the dynamical properties of the hydrated electron in cluster systems, the first principle dynamics using ab initio molecular dynamics and so on have been extensively applied. [135, 180, 371, 408, 446] They revealed information about the structure and relative stabilities of the isomer clusters. Nonadiabatic dynamics of a solvated electron in various photochemical processes has also been studied experimentally. [62, 123, 294, 329] Rossky and co-workers [327, 468] also studied the relaxation dynamics of excess electrons using quantum molecular dynamics simulation techniques. Here the nonadiabatic interactions were taken into account basically within the scheme of surface hopping technique. [444]... [Pg.283]

As a last example of a molecular system exhibiting nonadiabatic dynamics caused by a conical intersection, we consider a model that recently has been proposed by Seidner and Domcke to describe ultrafast cis-trans isomerization processes in unsaturated hydrocarbons [172]. Photochemical reactions of this type are known to involve large-amplitode motion on coupled potential-energy surfaces [169], thus representing another stringent test for a mixed quantum-classical description that is complementary to Models 1 and II. A number of theoretical investigations, including quantum wave-packet studies [163, 164, 172], time-resolved pump-probe spectra [164, 181], and various mixed... [Pg.259]