Reaction paths, potential energy surfaces examples

Theoretical predictions of potential energy surfaces and reaction paths can sometimes yield quite surprising results. In this section, we ll consider an example which illustrates the general approach toward and usefulness of studying potential energy surfaces in detail. 

Should a complete potential energy surface be subjected to outer and inner effects, then a new potential energy surface is obtained on which the corresponding rection paths can be followed. This is described in part 4.3.1 by the example of the potential energy surface of the system C2H5+ jC2H4 under solvent influence. After such calculations, reaction theory assertions concerning the reaction path and the similarity between the activated complex and educts or products respectively can be made. 

The first thing to be done when applying the theory is to identify the e and o reaction paths. One can then proceed to calculate and iPn, and then to extract If e and using Eq. (6). In H - - H2, the form of the potential energy surface is very well characterized [50-53], and the form of the Cl is a standard example of an E X e Jahn-Teller intersection. 

In the previous sections it has been implicitly assumed that the unimolecular reaction is electronically adiabatic and, thus, occurs on a single potential energy surface. Electronically excited states (i.e., multiple potential energy surfaces) for unimolecular reactions was discussed in chapter 3 and it is assumed that the reader has read and is familiar with this material (Nikitin, 1974 Hirst, 1985 Steinfeld et al., 1989). Transitions between electronic states are particularly important for the unimolecular decomposition of ions. For example, the following two dissociation paths ... 

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