Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations

Hiroshi Yamataka, Misako Aida, Michel Dupuis

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH2O.- with CH3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the SN2- like transition state (TS): (i) a direct formation of SN2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the SN2 valley. The direct formation of the ET product through the SN2-like TS appears to be more favorable at higher temperatures. The two-step process depends on the amount of energy that goes into the C-C stretching mode.

Original languageEnglish
Pages (from-to)310-316
Number of pages7
JournalChemical Physics Letters
Volume353
Issue number3-4
DOIs
Publication statusPublished - Feb 19 2002

Fingerprint

Stretching
Molecular dynamics
electron transfer
Substitution reactions
substitutes
Electrons
Computer simulation
products
simulation
Temperature
valleys
molecular dynamics
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations. / Yamataka, Hiroshi; Aida, Misako; Dupuis, Michel.

In: Chemical Physics Letters, Vol. 353, No. 3-4, 19.02.2002, p. 310-316.

Research output: Contribution to journalArticle

@article{933b30ca7f264daead9ade5034faaaba,
title = "Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations",
abstract = "Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH2O.- with CH3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the SN2- like transition state (TS): (i) a direct formation of SN2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the SN2 valley. The direct formation of the ET product through the SN2-like TS appears to be more favorable at higher temperatures. The two-step process depends on the amount of energy that goes into the C-C stretching mode.",
author = "Hiroshi Yamataka and Misako Aida and Michel Dupuis",
year = "2002",
month = "2",
day = "19",
doi = "10.1016/S0009-2614(02)00041-6",
language = "English",
volume = "353",
pages = "310--316",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "3-4",

}

TY - JOUR

T1 - Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations

AU - Yamataka, Hiroshi

AU - Aida, Misako

AU - Dupuis, Michel

PY - 2002/2/19

Y1 - 2002/2/19

N2 - Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH2O.- with CH3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the SN2- like transition state (TS): (i) a direct formation of SN2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the SN2 valley. The direct formation of the ET product through the SN2-like TS appears to be more favorable at higher temperatures. The two-step process depends on the amount of energy that goes into the C-C stretching mode.

AB - Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH2O.- with CH3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the SN2- like transition state (TS): (i) a direct formation of SN2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the SN2 valley. The direct formation of the ET product through the SN2-like TS appears to be more favorable at higher temperatures. The two-step process depends on the amount of energy that goes into the C-C stretching mode.

UR - http://www.scopus.com/inward/record.url?scp=0037133102&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037133102&partnerID=8YFLogxK

U2 - 10.1016/S0009-2614(02)00041-6

DO - 10.1016/S0009-2614(02)00041-6

M3 - Article

VL - 353

SP - 310

EP - 316

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 3-4

ER -