On the Theory of the Dissociation of Aromatic Radical Anions in Solution : A Ground Electronic State Conical Intersection Problem

摘要

Conical intersections (two electronic states which 'cross ' as a function of a certain coordinate but whose coupling is only finite-such that an avoided crossing is produced---due to motion in a second coordinate) have attracted considerable recent attention as 'funnels' for nonadiabatic transitions from excited electronic states to ground electronic states. There has however been almost no attention given to the influence of conical intersections on ground electronic state chemical reactions. Here we present what is evidently the first theoretical study of such a phenomenon. In particular, we will describe a theoretical study of the thermal unimolecular dissociation of aromatic radical anions in solution : [ArX].- →