New Diabatic Potential Energy Surfaces for the Li + H2 Reaction and Time-Dependent Quantum Wave Packet Studies.

Abstract

New global diabatic potential energy surfaces (DPESs) for the ground (12A') and first excited (22A') states for the Li + H2 system were developed, with more than 30,000 energy points at the IC-MRCI+Q level of theory, utilizing the aug-cc-pV5Z basis set for the H atoms and the cc-pCV5Z basis set for the Li atom, fitted by a single neural network (NN) with symmetry. Product state-resolved quantum dynamics calculations of the nonadiabatic reaction Li (2P) + H2 (X 1 ∑g+, v0 = 0, j0 = 0) → LiH (X 1∑+) + H(2S) were carried out using these new DPESs and also the previous HYLC-DPESs. The numerical results suggested that our newly constructed DPESs provided an accurate description of the LiH2 system.