Exploring Multiple Potential Energy Surfaces : Photochemistry of Small Carbonyl Compounds

Abstract EN

In theoretical studies of chemical reactions involving multiple potential energy surfaces (PESs) such as photochemical reactions, seams of intersection among the PESs often complicate the analysis.

In this paper, we review our recipe for exploring multiple PESs by using an automated reaction path search method which has previously been applied to single PESs.

Although any such methods for single PESs can be employed in the recipe, the global reaction route mapping (GRRM) method was employed in this study.

By combining GRRM with the proposed recipe, all critical regions, that is, transition states, conical intersections, intersection seams, and local minima, associated with multiple PESs, can be explored automatically.

As illustrative examples, applications to photochemistry of formaldehyde and acetone are described.

In these examples as well as in recent applications to other systems, the present approach led to discovery of many unexpected nonadiabatic pathways, by which some complicated experimental data have been explained very clearly.