Conical intersection intermediates

A photochemical reaction coordinate has two branches an excited state branch and a ground state branch that is reached after decay at a conical intersection. Thus a conical intersection between ground and excited states of a molecule is a precursor to ground state reactivity, and conforms to the above definition of a reactive intermediate. The main focus of our article will be to develop this idea. In Figure 9.1b, we show the energy profile for a photochemical reaction with a conical intersection... 

Figure 9.1. Energy profile for (a) a thermal reaction showing a high-energy intermediate, and (b) a photochemical reaction showing a conical intersection.

A simple example serves to illnstrate the similarities between a reaction mechanism with a conventional intermediate and a reaction mechanism with a conical intersection. Consider Scheme 9.2 for the photochemical di-tt-methane rearrangement. Chemical intnition snggests two possible key intermediate structures, II and III. Computations conhrm that, for the singlet photochemical di-Jt-methane rearrangement, structure III is a conical intersection that divides the excited-state branch of the reaction coordinate from the ground state branch. In contrast, structure II is a conventional biradical intermediate for the triplet reaction. 

Our hypothesis for discussion in this section has been that the conical intersection can be characterized like any other reactive intermediate. On examining Figure 9.3 or 9.10, it is clear that a conical intersection divides the excited-state branch of the reaction path from the ground-state branch in a photochemical transformation. (We shall... 

We hope that the preceding discussions have developed the concept of a conical intersection as being as real as many other reactive intermediates. The major difference compared with other types of reactive intermediate is that a conical intersection is really a family of structures, rather than an individual structure. However, the molecular structures corresponding to conical intersections are completely amenable to computation, even if their existence can only be inferred from experimental information. They have a well-defined geometry. Like the transition state, the crucial directions governing dynamics can be determined andX2) even if there are now two such directions rather than one. As for a transition structure, the nature of optimized geometries on the conical intersection hyperline can be determined from second derivative analysis. 

Such is the richness and intellectual vibrancy of the field of RI chemistry that an additional book was needed to cover silicon, germanium and tin centered RFs, as well as tetrahedral intermediates and topics of increasing importance such as quantum mechanical tunelling, conical intersections, solid-state chemistry, and combustion chemistry. These topics are covered in this new book. 

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