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Fast and reliable location of stationary points in a reaction path
Author(s) -
Cantillo David,
Ávalos Martín,
Babiano Reyes,
Cintas Pedro,
Jiménez José L.,
Palacios Juan C.
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1877
Subject(s) - saddle point , stationary point , chemistry , path (computing) , protocol (science) , function (biology) , potential energy surface , quantum , computational chemistry , statistical physics , algorithm , computer science , molecule , quantum mechanics , geometry , medicine , mathematical analysis , physics , mathematics , alternative medicine , organic chemistry , pathology , evolutionary biology , biology , programming language
This manuscript describes an easy, accurate, and expeditious methodology to locate all the stationary points in common organic reactions. The protocol is based on the analysis of potential energy surfaces (PES) by fitting the calculated data to a mathematical function. The method has been tested in several organic reactions, especially cycloadditions. In all cases, we succeeded in locating the bond parameters for the existing saddle points and intermediates, which were further corroborated by conventional geometry optimizations of the corresponding stationary points. Thus, the concerted or stepwise character of a typical cycloaddition can easily be predicted. It should be emphasized that this protocol is not intended to replace the current computational methodology to construct a PES, which is otherwise a long and rather tedious procedure, usually applied to very discrete molecular system. We prove instead that the present surrogate represents a valuable shortcut to identify stationary points at a given level of theory, which is in turn both reproducible and accurate and should be of interest to a large readership of practitioners engaged in mechanistic studies, who often fear quantum computational methods. Copyright © 2011 John Wiley & Sons, Ltd.