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
N1 - Funding Information:
The calculations were carried out in part at the Computer Center of the Institute for Molecular Science. This work is supported in part by the Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan. MD was supported by the U.S. Department of Energy's Office of Biological and Environmental Research, and the Office of Basic Energy Sciences, Chemical Physics Program. The Pacific Northwest National Laboratory is a multi-program national laboratory operated for the U.S. Department of Energy by Battelle Memorial Institute under Contract DE-AC06-76RLO 1830.
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.
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U2 - 10.1016/S0009-2614(02)00041-6
DO - 10.1016/S0009-2614(02)00041-6
M3 - Article
AN - SCOPUS:0037133102
VL - 353
SP - 310
EP - 316
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 3-4
ER -