Full-dimensional quantum dynamics study of the H-2 + C2H - H + C2H2 reaction on an ab initio potential energy surface

摘要

This work performs a time-dependent wavepacket study of the H-2 + C2H -> H + C2H2 reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H-2 + C2H <-> H + C2H2, H + C2H2 -> HCCH2, and HCCH2 radial isomerization reaction regions. The reaction dynamics of H-2 + C2H -> H + C2H2 are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H-2 vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C2H slightly inhibits the reaction. The excitations of two stretching modes of C2H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values. Published by AIP Publishing.