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

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 (PIP-NN) method based on 30,974 points whose energies are calculated at the CCSD(T)-F12a/AVTZ level. Then Ring Polymer Molecular Dynamics (RPMD) is used to derive the free energy barrier of the reaction at the experimental temperature range, 472.55 ~ 532.92 K. Reaction kinetics are studied in the high-pressure limit and in the fall-off region by standard transition state theory and master equation, respectively. The calculated temperature- and pressure-dependent rate coefficients are in good agreement with previous experimental and theoretical results. Further, Quasi-Classical Trajectory (QCT) 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.