TY - JOUR
T1 - N + CN → C + N 2
T2 - A global potential energy surface, entrance channel recrossing and the applicability of capture theory
AU - Frankcombe, Terry J.
AU - McNeil, Steven D.
AU - Nyman, Gunnar
PY - 2011/9/27
Y1 - 2011/9/27
N2 - A global potential energy surface for the CN2 system has been developed with the aim of studying the N+CN→C+N2 reaction at low temperatures. A three-dimensional analytic functional form has been fit to CASPT3/cc-pVQZ energies. Classical trajectory simulations on this fitted representation of the potential show a significant proportion of trajectories returning to the entrance channel after forming the CN2 intermediate, violating a key assumption of capture theory. While the fitted potential is considered inappropriate for calculating accurate low-temperature thermal rate constants, the potential can be used in future studies of the poorly characterised N+CN and C+N2 reactions at temperatures relevant to combustion.
AB - A global potential energy surface for the CN2 system has been developed with the aim of studying the N+CN→C+N2 reaction at low temperatures. A three-dimensional analytic functional form has been fit to CASPT3/cc-pVQZ energies. Classical trajectory simulations on this fitted representation of the potential show a significant proportion of trajectories returning to the entrance channel after forming the CN2 intermediate, violating a key assumption of capture theory. While the fitted potential is considered inappropriate for calculating accurate low-temperature thermal rate constants, the potential can be used in future studies of the poorly characterised N+CN and C+N2 reactions at temperatures relevant to combustion.
UR - http://www.scopus.com/inward/record.url?scp=80052950782&partnerID=8YFLogxK
U2 - 10.1016/j.cplett.2011.08.047
DO - 10.1016/j.cplett.2011.08.047
M3 - Article
SN - 0009-2614
VL - 514
SP - 40
EP - 43
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-3
ER -