Minimum energy path chemical reactions

In the chapter on reaction rates, it was pointed out that the perfect description of a reaction would be a statistical average of all possible paths rather than just the minimum energy path. Furthermore, femtosecond spectroscopy experiments show that molecules vibrate in many dilferent directions until an energetically accessible reaction path is found. In order to examine these ideas computationally, the entire potential energy surface (PES) or an approximation to it must be computed. A PES is either a table of data or an analytic function, which gives the energy for any location of the nuclei comprising a chemical system. 

MEP (IRC, intrinsic reaction coordinate, minimum-energy path) the lowest-energy route from reactants to products in a chemical process MIM (molecules-in-molecules) a semiempirical method used for representing potential energy surfaces... 

In most cases, the observables measured in the study of a chemical reaction are interpreted under the following (often valid) assumptions (1) each product channel observed corresponds to one path on the PES, (2) reactions follow the minimum energy path (MEP) to each product channel, and (3) the reactive flux passes over a single, well-defined transition state. In all of the reactions discussed in this chapter, at least one, and sometimes all of these assumptions, are invalid. 

A very perceptive treatment of chemical reaction dynamics, called the reaction path Hamiltonian analysis, states that the reactive trajectory is determined as the minimum energy path, and small displacements from that path, on the potential-energy surface [64-71]. The usual analysis keeps the full dimensionality of the reacting system, albeit with a focus on motion along and orthogonal to the minimum energy path. It is also possible to define a reaction path in a reduced dimensionality representation. 

One of the most useful static methods of microscopic chemical kinetics is based on the definition of the reaction path as introduced by Fukui. This method offers information on reactions in terms of the intrinsic reaction coordinate (62,144). A theoretical analysis of the minimum energy path was given in Section III,B. Fukui s definition is equivalent to Eq. (34). 

Energy derivatives are essential for the computation of dynamics properties. There are several dynamics-related methods available in gamess. The intrinsic reaction coordinate (IRC) or minimum energy path (MEP) follows the infinitely damped path from a first-order saddle point (transition state) to the minima connected to that transition state. In addition to providing an analysis of the process by which a chemical reaction occurs (e.g. evolution of geometric structure and wavefunction), the IRC is a common starting point for the study of dynamics. Example are variational transition state theory (VTST [55]) and the modified Shepard interpolation method developed by Collins and co-workers... 

The first aim of a theoretical study of a chemical reaction is to determine the reaction mechanism that corresponds to the minimum energy path that connects the minima of reactant and products and passes through the transition state (TS) structures on the potential en-... 

Fig. 1. Schematic representation of the structure of the potential-energy surface for a thermal chemical reaction. The dashed curve indicates the minimum-energy path, ini and Min2 are local energy minima corresponding to reactants and products. TS is a saddle point corresponding to the transition structure. IVlax is a local maximum.

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