Nonadiabatic quantum reactive scattering of the OH (A ~2∑ ~+) + D_2

摘要

The seams of conical intersection exist between the ground (1 ~2A′) and the first-excited (2 ~2A′) electronic potential energy surfaces (PESs) of OH (A ~2∑~+,X ~2Π) + H_2 system. This intersection induces the nonadiabatic quenching of OH (A ~2∑ ~+) by D _2. We present nonadiabatic quantum dynamics study for OH (A ~2∑~+) + D_2 on new five-dimensional coplanar PESs. The ab initio calculations of PESs are based on multireference configuration interaction (MRCI)/aug-cc-pVQZ level. A back-propagation neural network is utilized to fit the PESs and nonadiabatic coupling. High degrees of rotational excitation of quenched OH (X ~2Π) products are found in nonreactive quenching channel, and the quenched D_2 products are vibrationally excited up to quantum number v_2′ =8. The theoretical results of nonadiabatic time-dependent wave-packet calculation are in good agreement with the existing experimental data.