Projectdescription.docVIP

The “Chemistry” of Conical Intersections # 1. Introduction. The Quest for the Photochemical “Funnel” With their seminal 1935 work on the structure of potential energy surfaces, Eyring1, Evans and Polaniy2 were able to define the exact nature of the “activated complex” or “transition state” for ordinary (thermal) chemical reactions. The molecular structure of a transition state describes the spatial arrangement of the atoms corresponding to the highest point (TS) on the potential energy surface that has to be overcome by the reactant to form the product. This discovery not only provided the basic “conceptual tool” for understanding chemical reactivity, but also indicated the way for getting, through quantum chemical calculations, information on the molecular structure of the transition state. Furthermore the full reaction path can be determined by computing the minimum energy path (see dashed line in Figure 1): the curve that connects the transition state structure TS (a saddle point on the potential energy surface) with the energy minima associated with the reactant (Min1) and the product (Min2). The successful development of quantum chemistry packages and the availability of increasingly fast computers in more recent years have made the computational investigation of thermal reaction paths a routine practice in the modern chemical laboratory. Before our project started the computations of photochemical reaction paths was unpractical if not impossible. In a photochemical reaction the reactant is an electronically excited state molecule or complex M* while the product is a ground state species. Thus, in order to describe a photochemical reaction, one must first establish the nature of the spatial arrangement of the atoms corresponding to the point where M* decays from the excited state potential energy surface to the ground state and initiate product formation. Loosely, this critical molecular structure plays the role of the “transition state” for a photochemical p