The C(P-3) + NO(X-2 Pi) - O(P-3) + CN(X-2 Sigma(+)), N(D-2)/N(S-4) + CO(X-1 Sigma(+)) reaction: Rates, branching ratios, and final states from 15 K to 20 000 K

摘要

The C + NO collision system is of interest in the area of high-temperature combustion and atmospheric chemistry. In this work, full dimensional potential energy surfaces for the (2)A', (2)A '', and (4)A '' electronic states of the [CNO] system have been constructed following a reproducing kernel Hilbert space approach. For this purpose, more than 50 000 ab initio energies are calculated at the MRCI+Q/aug-cc-pVTZ level of theory. The dynamical simulations for the C(P-3) + NO(X-2 Pi) - O(P-3) + CN(X-2 Sigma(+)), N(D-2)/N(S-4) + CO(X-1 Sigma(+)) reactive collisions are carried out on the newly generated surfaces using the quasiclassical trajectory (QCT) calculation method to obtain reaction probabilities, rate coefficients, and the distribution of product states. Preliminary quantum calculations are also carried out on the surfaces to obtain the reaction probabilities and compared with QCT results. The effect of nonadiabatic transitions on the dynamics for this title reaction is explored within the Landau-Zener framework. QCT simulations have been performed to simulate molecular beam experiment for the title reaction at 0.06 and 0.23 eV of relative collision energies. Results obtained from theoretical calculations are in good agreement with the available experimental as well as theoretical data reported in the literature. Finally, the reaction is studied at temperatures that are not practically achievable in the laboratory environment to provide insight into the reaction dynamics at temperatures relevant to hypersonic flight. Published by AIP Publishing.