Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

被引：12

作者：

Minyaev, Ruslan M. ^{[1
]}

Quapp, Wolfgang ^{[2
]}

Schmidt, Benjamin ^{[2
]}

Getmanskii, Ilya V. ^{[1
]}

Koval, Vitaliy V. ^{[1
]}

机构：

[1] Southern Fed Univ, Inst Phys & Organ Chem, Rostov Na Donu 344090, Russia

[2] Univ Leipzig, Math Inst, D-04109 Leipzig, Germany

来源：

CHEMICAL PHYSICS | 2013年 / 425卷

基金：

俄罗斯基础研究基金会;

关键词：

Coupled cluster calculations; Density functional theory; Potential energy surface; Second order stationary point; Reaction path; RIDGE INFLECTION POINTS; POTENTIAL-ENERGY SURFACES; GRADIENT LINE; GAS-PHASE; COORDINATE; SEARCH; SET;

D O I：

10.1016/j.chemphys.2013.08.014

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Quantum chemical (CCSD(full)/6-311++ G(3df, 3pd), CCSD(T)(full)/6-311++ G(3df, 3pd)) and density function theory (B3LYP/6-311++ G(3df, 3pd)) calculations were performed for the S(N)2 nucleophile substitution reactions CH4 + H -> CH4 + H and CH4 + F -> CH3F + H. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches. (C) 2013 Elsevier B. V. All rights reserved.

引用

页码：170 / 176

页数：7

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