TY - JOUR
T1 - Central barrier recrossing dynamics of the Cl-+CD3Cl SN2 reaction
AU - Cheon, Sueun
AU - Song, Kihyung
AU - Hase, William L.
N1 - Funding Information:
This material is based upon work supported by the National Science Foundation under Grants Nos. 0315614 and 0412677, and by the Robert A. Welch Foundation.
PY - 2006/10/12
Y1 - 2006/10/12
N2 - A direct dynamics simulation, at the MP2/6-31G* level of theory, was performed for the Cl-+CD3Cl SN2 reaction. An ensemble of 88 trajectories was initiated at the [Cl- -CD3- -Cl]- central barrier, in accord with a 300 K Boltzmann distribution, and integrated in both the forward and reverse directions off the barrier. The dynamics of these trajectories are inconsistent with both RRKM theory and transition state theory (TST). Only 1% of the trajectories dissociate to Cl-+CD3Cl products in comparison to the RRKM prediction of greater than 50%. Also, in contrast to the assumption of TST and prediction of RRKM theory, recrossings of the central barrier are observed in the trajectories, giving rise to an upper limit of 0.7 for the correction factor to the 300 K TST rate constant. The results of this study are compared with a previous direct dynamics simulation, also at the MP2/6-31G* level of theory, of the central barrier dynamics for the Cl-+CH3Cl SN2 reaction. Both reactions exhibit extensive non-RRKM dynamics. However, central barrier recrossings are more important for the Cl-+CH3Cl reaction and the upper limit to its TST correction factor is 0.2.
AB - A direct dynamics simulation, at the MP2/6-31G* level of theory, was performed for the Cl-+CD3Cl SN2 reaction. An ensemble of 88 trajectories was initiated at the [Cl- -CD3- -Cl]- central barrier, in accord with a 300 K Boltzmann distribution, and integrated in both the forward and reverse directions off the barrier. The dynamics of these trajectories are inconsistent with both RRKM theory and transition state theory (TST). Only 1% of the trajectories dissociate to Cl-+CD3Cl products in comparison to the RRKM prediction of greater than 50%. Also, in contrast to the assumption of TST and prediction of RRKM theory, recrossings of the central barrier are observed in the trajectories, giving rise to an upper limit of 0.7 for the correction factor to the 300 K TST rate constant. The results of this study are compared with a previous direct dynamics simulation, also at the MP2/6-31G* level of theory, of the central barrier dynamics for the Cl-+CH3Cl SN2 reaction. Both reactions exhibit extensive non-RRKM dynamics. However, central barrier recrossings are more important for the Cl-+CH3Cl reaction and the upper limit to its TST correction factor is 0.2.
KW - Direct Dynamics
KW - S2 Dynamics
KW - Trajectories
UR - http://www.scopus.com/inward/record.url?scp=33749143641&partnerID=8YFLogxK
U2 - 10.1016/j.theochem.2006.03.032
DO - 10.1016/j.theochem.2006.03.032
M3 - Article
AN - SCOPUS:33749143641
SN - 0166-1280
VL - 771
SP - 27
EP - 31
JO - Journal of Molecular Structure: THEOCHEM
JF - Journal of Molecular Structure: THEOCHEM
IS - 1-3
ER -