TY - JOUR
T1 - Perspective
T2 - Chemical dynamics simulations of non-statistical reaction dynamics
AU - Ma, Xinyou
AU - Hase, William L.
N1 - Funding Information:
The atomistic simulations for the Hase research group are supported by the National Science Foundation under grant no. CHE-1416428, the Robert A. Welch Foundation under grant no. D-0005 and the Air Force Office of Scientific Research under AFOSR Award no. FA9550-16-1-0133.
PY - 2017/4/28
Y1 - 2017/4/28
N2 - Non-statistical chemical dynamics are exemplified by disagreements with the transition state (TS), RRKM and phase space theories of chemical kinetics and dynamics. The intrinsic reaction coordinate (IRC) is often used for the former two theories, and nonstatistical dynamics arising from non-IRC dynamics are often important. In this perspective, non-statistical dynamics are discussed for chemical reactions, with results primarily obtained from chemical dynamics simulations and to a lesser extent from experiment. The non-statistical dynamical properties discussed are: post-TS dynamics, including potential energy surface bifurcations, product energy partitioning in unimolecular dissociation and avoiding exitchannel potential energy minima; non-RRKM unimolecular decomposition; non-IRC dynamics; direct mechanisms for bimolecular reactions with preand/ or post-reaction potential energy minima; non-TS theory barrier recrossings; and roaming dynamics.
AB - Non-statistical chemical dynamics are exemplified by disagreements with the transition state (TS), RRKM and phase space theories of chemical kinetics and dynamics. The intrinsic reaction coordinate (IRC) is often used for the former two theories, and nonstatistical dynamics arising from non-IRC dynamics are often important. In this perspective, non-statistical dynamics are discussed for chemical reactions, with results primarily obtained from chemical dynamics simulations and to a lesser extent from experiment. The non-statistical dynamical properties discussed are: post-TS dynamics, including potential energy surface bifurcations, product energy partitioning in unimolecular dissociation and avoiding exitchannel potential energy minima; non-RRKM unimolecular decomposition; non-IRC dynamics; direct mechanisms for bimolecular reactions with preand/ or post-reaction potential energy minima; non-TS theory barrier recrossings; and roaming dynamics.
KW - Chemical reaction dynamics
KW - Non-intrinsic reaction coordinate dynamics
KW - Non-statistical dynamics
KW - Post-transition state dynamics
UR - http://www.scopus.com/inward/record.url?scp=85015888970&partnerID=8YFLogxK
U2 - 10.1098/rsta.2016.0204
DO - 10.1098/rsta.2016.0204
M3 - Review article
C2 - 28320906
AN - SCOPUS:85015888970
SN - 1364-503X
VL - 375
JO - Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
JF - Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
IS - 2092
M1 - 20160204
ER -