Title of Paper:A new potential energy surface of LiHCl system and dynamic studies for the Li(S-2) + HCl(X-1 Sigma(+)) -> LiCl(X-1 Sigma(+)) + H(S-2) reaction

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Date of Publication:2016-12-21

Journal:JOURNAL OF CHEMICAL PHYSICS

Included Journals:SCIE、EI、PubMed、Scopus

Volume:145

Issue:23

Page Number:234312

ISSN No.:0021-9606

Abstract:A new global potential energy surface (PES) is constructed for the ground state of LiHCl system based on high-quality ab initio energy points calculated using multi-reference configuration interaction calculations with the Davidson correction. The AVQZ and WCVQZ basis sets are employed for H and Li atoms, respectively. To compensate the relativistic effects of heavy element, theAWCVQZ-DK basis set is employed for Cl atom. The neural network method is used for fitting the PES, and the root mean square error is small (1.36 x 10(-2) eV). The spectroscopic constants of the diatoms obtained from the new PES agree well with experimental data. The geometric characteristics of the transition state and the complex are examined and compared with the previous theoretical values. To study the reaction dynamics of the Li(S-2) + HCl(X-1 Sigma(+)) -> LiCl(X-1 Sigma(+)) + H(S-2) reaction, quantum reactive scattering dynamics calculations using collection reactant-coordinate-based wave packet method are conducted based on the new PES. The results of the reaction probabilities indicate that a small barrier exists along the reaction path as observed from the PES. The integral cross section curves reveal that the product molecule LiCl is easily excited. In addition, the reaction is dominated by forward scattering, and similar pattern is observed from Becker's experiment. Published by AIP Publishing.