Role of conical intersections in molecular spectroscopy and photoinduced chemical dynamics

This review describes how conical intersections affect measured molecular spectra and simple photofragmentation processes. We consider excitations that result in electron ejection, that is, photoionization or photodetachment, as well as photoinduced H-atom elimination. Section 1 presents a brief overview of the history of conical intersections and their rise from an arcane theoretical concept to a major paradigm in nonadiabatic chemistry. In Section 2, the generic properties of conical intersections are discussed, as well as their characterization with modern electronic-structure methods. Section 3 briefly discusses computational tools used to compute the nuclear motion involving conical intersections. Section 4 describes how the ideas of Sections 2 and 3 are combined to simulate molecular spectra impacted by conical intersections. Section 5 describes selected recent experimental and computational studies of photoelectron, photodetachment, and photofragment spectra. Rather than providing an encyclopedic bibliography of the previous and current literature, we illustrate significant problems currently being addressed and describe what can be accomplished with current computational techniques and how these results are achieved. Section 6 suggests future directions in this field.