Chemistry of Excited Electronic States

Atomic and molecular orbitals are among the tools used by chemists to view the world. The validity of this view for reaction systems can be experimentally probed by examination of the chemistry of electronically excited states and, in particular, by comparison of the reactivities of states having different orbital occupations (electron configurations). Reactivity changes associated with electron configuration are instructive with regard to chemists' views of molecular orbital interactions, but electronic excitation can also influence the course of a chemical reaction by increasing the energy content of the system or by affecting access to different potential energy surfaces by changing spin, orbital symmetry, or spin-orbit level. These various effects are illustrated by studies of gasphase transition metal-mediated H-H and C-H bond-activation processes.