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Nontotally symmetric trifurcation of an S N 2 reaction pathway
Author(s) -
Harabuchi Yu,
Ono Yuriko,
Maeda Satoshi,
Taketsugu Tetsuya,
Keipert Kristopher,
Gordon Mark S.
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24241
Subject(s) - saddle point , maxima and minima , inflection point , chemistry , symmetry (geometry) , curvature , branching (polymer chemistry) , path (computing) , physics , combinatorics , geometry , mathematics , mathematical analysis , organic chemistry , computer science , programming language
A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical S N 2‐type reaction, NC ‐ + CH 3 X → NCCH 3 + X ‐ (X = F, Cl). A nontotally symmetric valley‐ridge inflection (VRI) point was located along the C 3 v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second‐order saddle point with C 3 v symmetry, which connects three product minima of C s symmetry. For X = Cl, four product minima have been observed, of which three belong to C s symmetry and one to C 3 v symmetry. The branching path from the VRI point to the lower symmetry minima was determined by a linear interpolation technique. The branching mechanism is discussed based on the reaction path curvature and net atomic charges, and the possibility of a nonotally symmetric n‐furcation is discussed. © 2015 Wiley Periodicals, Inc.