Thermal Rate Constants for the O(P-3) + CH4 - OH + CH3 Reaction: The Effects of Quantum Tunneling and Potential Energy Barrier Shape

摘要

The rate constants and kinetic isotope effects for the O(P-3) + CH4 reaction have been investigated with the quantum instanton method in full dimensionality. The calculated rate constants, are in good agreement with the experimental values above 400 K, below which the measured values are scattered. Compared to other theoretical approaches, the quantum instanton method predicts the largest quantum tunneling effect, so it gives the largest rate constants at low temperatures. The calculated kinetic isotope effects are always much larger than 1 and increase with decreasing temperature, due to the zero-point energy and quantum tunneling. Our calculations on different potential energy surfaces demonstrate that the potential energy barrier shape dominates the magnitude of quantum tunneling and has a great effect on the kinetic isotope effect.