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

共 50 条

[31] THE MECHANISM OF THE REACTION CH4(+)+CH4 = CH5(+)+CH3 AS A FUNCTION OF ENERGY - RATE CONSTANTS AND PRODUCT DISTRIBUTIONS FOR THE REACTIONS OF CH4(+)+CD4 AND CD4(+)+CH4 AT 80-K AND 300-K
HENCHMAN, M
SMITH, D
ADAMS, NG
PAULSON, JF
HERMAN, Z
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY, 1989, 92 : 15 - 36
[32] Construction of F-containing porous organic framework with low CH4 uptake and high C3H8/CH4
Wang, Shanshan
Gao, Xinyue
Zheng, Bo
Ma, Heping
Ren, Hao
SEPARATION AND PURIFICATION TECHNOLOGY, 2025, 361
[33] Thermodynamic Analysis of a Regenerative Brayton Cycle Using H2, CH4 and H2/CH4 Blends as Fuel
Lopez-Ruiz, Gontzal
Castresana-Larrauri, Joseba
Maria Blanco-Ilzarbe, Jesus
ENERGIES, 2022, 15 (04)
[34] Reprint of: CO2/CH4, CH4/H2 and CO2/CH4/H2 separations at high pressures using Mg2(dobdc)
Herm, Zoey R.
Krishna, Rajamani
Long, Jeffrey R.
MICROPOROUS AND MESOPOROUS MATERIALS, 2012, 157 : 94 - 100
[35] The effects of CO addition on the autoignition of H2, CH4 and CH4/H2 fuels at high pressure in an RCM
Gersen, Sander
Darmeveil, Harry
Levinsky, Howard
COMBUSTION AND FLAME, 2012, 159 (12) : 3472 - 3475
[36] INFLUENCE OF EXHAUST GAS RECIRCULATION ON COMBUSTION INSTABILITIES IN CH4 AND H2/CH4 FUEL MIXTURES
Ferguson, Don
Ranalli, Joseph A.
Strakey, Peter
PROCEEDINGS OF THE ASME TURBO EXPO 2010, VOL 2, PTS A AND B, 2010, : 1259 - 1267
[37] Rovibrational energy and spectroscopic constant calculations of CH 4 ⋯ CH4, CH 4 ⋯ H2 O, CH 4 ⋯ CHF3, and H 2O ⋯ CHF3 dimers
Wiliam F. Cunha
Ricardo Gargano
Edgardo Garcia
José R. S. Politi
Alessandra F. Albernaz
João B. L. Martins
Journal of Molecular Modeling, 2014, 20
[38] KINETICS OF CH4 FORMATION FROM REACTION OF H WITH GRAPHITE
GOULD, RK
JOURNAL OF CHEMICAL PHYSICS, 1975, 63 (05): : 1825 - 1836
[39] Single- and double-electron loss of H- in collisions with SF6, CH4, and CO
Dominguez, I
deUrquijo, J
Cisneros, C
Martinez, H
Alvarez, I
PHYSICAL REVIEW A, 1996, 54 (01) : 506 - 509
[40] ON THE FORMATION OF C2H8(+) IN THE REACTION CH4(+)+CH4-]CH3+CH5(+) - A THEORETICAL-STUDY
HAVLAS, Z
BAUWE, E
ZAHRADNIK, R
CHEMICAL PHYSICS LETTERS, 1985, 121 (4-5) : 330 - 333

← 1 2 3 4 5 →