%0 Journal Article
%T Exploring Multiple Potential Energy Surfaces: Photochemistry of Small Carbonyl Compounds
%A Satoshi Maeda
%A Koichi Ohno
%A Keiji Morokuma
%J Advances in Physical Chemistry
%D 2012
%I Hindawi Publishing Corporation
%R 10.1155/2012/268124
%X 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. 1. Introduction In order to theoretically unravel the entire photochemical reaction processes of a given system, one has to explore and characterize systematically several excited as well as the ground state potential energy surfaces (PESs). In the Franck-Condon (FC) approximation, a reaction starts from the FC point on an excited state PES. Then, the system undergoes either adiabatic or nonadiabatic pathways depending on a given excess energy and topographies on the PESs. In adiabatic paths, a bond reorganization occurs directly on the excited state PES through transition states (TSs). In nonadiabatic paths, on the other hand, the system makes nonadiabatic transition to a lower PES and then reacts on the lower PES. The system may cascade through several PESs via nonadiabatic transitions. Seams of intersection between two PESs often play a key role in various reactions [1¨C7]; near an intersection seam, nonadiabatic transitions can take place efficiently. When the two states have the same spin and space symmetry, the intersection hyperspace consists of f-2 dimensions and is called ¡°conical intersection (CI),¡± where f is the number of vibrational degrees of freedom. If the spin multiplicity and/or the space symmetry are different, the PESs cross simply in f-1 dimensional hyperspace. In this paper, both of these two types of intersections, that is, conical intersection and simple intersection seam, are denoted as ¡°seam-of-crossing.¡± In many kinetic studies, minimum energy structures on seam-of-crossing hyperspaces (MSXs)
%U http://www.hindawi.com/journals/apc/2012/268124/