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

Hiroshi Yamataka; Misako Aida; Michel Dupuis

doi:10.1016/S0009-2614(02)00041-6

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

Hiroshi Yamataka, Misako Aida, Michel Dupuis

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

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 S_N2- like transition state (TS): (i) a direct formation of S_N2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the S_N2 valley. The direct formation of the ET product through the S_N2-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 language	English
Pages (from-to)	310-316
Number of pages	7
Journal	Chemical Physics Letters
Volume	353
Issue number	3-4
DOIs	https://doi.org/10.1016/S0009-2614(02)00041-6
Publication status	Published - Feb 19 2002

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ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

Cite this

Yamataka, H., Aida, M., & Dupuis, M. (2002). Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations. Chemical Physics Letters, 353(3-4), 310-316. https://doi.org/10.1016/S0009-2614(02)00041-6

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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.

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10.1016/S0009-2614(02)00041-6