Quantum dynamics study of H2+CN → HCN+H reaction in full dimensions

Abstract

Time-dependent (TD) quantum dynamics calculation for the title reaction has been carried out in full mathematical (six) dimensions on a new potential energy surface (denoted TSH3). Our numerical calculation shows that as far as total reaction probabilities and cross sections are concerned, the CN vibration behaves like a spectator bond when both reagents are at ground vibrational state. The vibrational excitation of CN slightly decreases the reaction probability and cross section while vibrational excitation of H2 considerably enhances the reaction probability and cross section. The reaction probability is enhanced by excitations of H2 rotation and more so of CN rotation. Overall, the reaction proceeds by a direct abstraction path without contribution from the insertion process. Comparison of our calculated rate constant with experimental measurements indicates that the effective barrier of the TSH3 PES for the title reaction is perhaps too high by about 0.3 kcal/mol.