Abstract
The global diabatic potential energy surfaces which are correlated with the ground state 1A′ and the excited state 2A′ of the Li(2p) + H2 reaction are presented in this study. The multi-reference configuration interaction method and large basis sets (aug-cc-pVQZ for H atom and cc-pwCVQZ for Li atom) were employed in the ab initio single-point energy calculations. The diabatic potential energies were generated by the diabatization scheme based on transition dipole moment operators. The neural network method was utilized to fit the matrix elements of the diabatic energy surfaces, and the root mean square errors were extremely small (3.69 meV for , 5.34 meV for and 5.06 meV for ). The topographical features of the diabatic potential energy surfaces were characterized and the surfaces were found to be sufficiently smooth for the dynamical calculation. The crossing seam of the conical intersections between the and surfaces were pinpointed. Based on this new analytical diabatic potential energy surfaces, time-dependent wave packet calculation were conducted to investigate the mechanism of the title reaction. At low collision energies, the product LiH molecule tends to forward scattering, while at high collision energies, the forward and backward scatterings exist simultaneously.
Highlights
Many experimental studies have focused on the Li(2p) + H2(X1Σ +g) → LiH(X1Σ +) + H reaction, few theoretical studies of this reaction have been reported[22,23]
It can be seen from this figure that in the vicinity of the crossing point, the change rate of the mixing angle becomes steeper with the increase of θ
The diabatization scheme is based on www.nature.com/scientificreports/ Figure 7
Summary
Many experimental studies have focused on the Li(2p) + H2(X1Σ +g) → LiH(X1Σ +) + H reaction, few theoretical studies of this reaction have been reported[22,23]. The PES used in their research is limited to three different point group symmetries: C∞v, C2v and Cs where the molecular axis of the H2 molecule makes an angle of π /4 with respect to the velocity vector of the lithium atom Since this PES is not global, it cannot accurately describe all the features of the intermolecular interaction potential of the Li(2p) + H2 reaction. For the title reaction, there are no such a set of diabatic PESs that can be employed for dynamical calculations To meet these requirements above mentioned, a set of global diabatic PESs was constructed for the lowest two 2A′ states of LiH2 system using the neural network (NN) method[25]. Based on the diabatic PESs, the reaction dynamics of the title reaction were investigated using the TDWP method
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