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Nontotally symmetric trifurcation of an SN2 reaction pathway.

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Bibliographic Details
Title:	Nontotally symmetric trifurcation of an SN2 reaction pathway.
Authors:	Harabuchi, Yu¹, Ono, Yuriko¹, Maeda, Satoshi¹, Taketsugu, Tetsuya¹, Keipert, Kristopher², Gordon, Mark S.²
Source:	Journal of Computational Chemistry. Feb2016, Vol. 37 Issue 5, p487-493. 7p.
Subjects:	Bifurcation theory, Minimum energy reaction path, Hessian matrices, Transition state theory (Chemistry), Saddlepoint approximations
Abstract:	A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN2-type reaction, NC- + CH3X → NCCH3 + X- (X = F, Cl). A nontotally symmetric valley-ridge inflection (VRI) point was located along the C3 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 C3 v symmetry, which connects three product minima of Cs symmetry. For X = Cl, four product minima have been observed, of which three belong to Cs symmetry and one to C3 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. [ABSTRACT FROM AUTHOR]
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Database:	Engineering Source

Description
Abstract:	A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN2-type reaction, NC- + CH3X → NCCH3 + X- (X = F, Cl). A nontotally symmetric valley-ridge inflection (VRI) point was located along the C3 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 C3 v symmetry, which connects three product minima of Cs symmetry. For X = Cl, four product minima have been observed, of which three belong to Cs symmetry and one to C3 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. [ABSTRACT FROM AUTHOR]
ISSN:	01928651
DOI:	10.1002/jcc.24241