Full-dimensional accurate potential energy surface and dynamics for the unimolecular isomerization reaction CH3NC ⇌ CH3CN

Abstract

The reaction CH3NC ⇌ CH3CN, a model reaction for the study of unimolecular isomerization, is important in astronomy and atmospheric chemistry and has long been studied by numerous experiments and theories. In this work, we report the first full-dimensional accurate potential energy surface (PES) of this reaction by the permutation invariant polynomial-neural network method based on 30 974 points, whose energies are calculated at the CCSD(T)-F12a/AVTZ level. Then, ring polymer molecular dynamics is used to derive the free energy barrier of the reaction at the experimental temperature range of 472.55–532.92 K. Reaction kinetics are studied at the high-pressure limit and in the fall-off region by standard transition state theory and the master equation, respectively. The calculated temperature- and pressure-dependent rate coefficients are in good agreement with previous experimental and theoretical results. Furthermore, quasi-classical trajectory simulations are performed on this PES to study the intramolecular energy transfer dynamics at initial vibrational energies of 4.336, 5.204, and 6.505 eV.