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Intrinsic reaction coordinate of perturbed potential energy surfaces: Construction of perturbed energy profiles
Author(s) -
Mestres Jordi,
Duran Miquel
Publication year - 1993
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560470404
Subject(s) - reaction coordinate , inversion (geology) , chemistry , ab initio , potential energy , coordinate system , computational chemistry , potential field , atomic physics , physics , geometry , mathematics , paleontology , organic chemistry , structural basin , geophysics , biology
This contribution analyzes the changes in the intrinsic reaction coordinate ( IRC ) and in the potential energy profiles ( PEP ) caused by application of a uniform electric field evaluated using standard ab initio MO methods. Two typical organic processes have been studied, namely, the Friedel–Crafts and the Walden inversion reactions, which are modeled by suitable simple systems. The results for the Walden inversion reaction show that the IRC for the field‐free and that for perturbed processes are almost coincident; in this case, using the field‐free IRC to compute the perturbed energy profile is a very good approximation. On the contrary, for the Friedel–Crafts model reaction, the two IRC s differ slightly, so the energy profiles using the perturbed and the unperturbed IRC s are somewhat different. © 1993 John Wiley & Sons, Inc.