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Title: A new potential energy surface and state-to-state quantum dynamics of the $$\mathrm{Li + HF → H + LiF}$$ reaction

Abstract

A new global potential energy surface (PES) for the ground ($$\tilde{X}^2A'$$) state of the Li + HF → LiF + H reactive system is constructed by fitting 12,399 points computed at the UCCSD(T)-F12b/aug-cc-pV5Z level of theory. The use of a neural network method helps to achieve a high-fidelity fit with a root mean square error of 0.88 meV. Quantum dynamics calculations with full Coriolis coupling on the new PES yield both differential and integral cross sections over a range of energy. In agreement with experiment, the product angular distribution depends sensitively on collision energy, but all with a forward bias. Moderate internal excitation is found in the LiF product. The energy dependence of the integral cross section is in reasonably good accord with the experimental excitation function, although some quantitative differences persist. This late-barrier reaction shows a dramatic vibrational enhancement of reactivity. The mode specificity is rationalized using the Sudden Vector Projection model.

Authors:
 [1];  [1];  [1]
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  1. University of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); Shandong Provincial Governmental
OSTI Identifier:
1538098
Alternate Identifier(s):
OSTI ID: 1593490
Grant/Contract Number:  
SC0015997; 11274205
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Physics
Additional Journal Information:
Journal Volume: 509; Journal Issue: C; Journal ID: ISSN 0301-0104
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Xinguo, Xie, Changjian, and Guo, Hua. A new potential energy surface and state-to-state quantum dynamics of the $\mathrm{Li + HF → H + LiF}$ reaction. United States: N. p., 2018. Web. doi:10.1016/j.chemphys.2018.01.023.
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Liu, Xinguo, Xie, Changjian, & Guo, Hua. A new potential energy surface and state-to-state quantum dynamics of the $\mathrm{Li + HF → H + LiF}$ reaction. United States. https://doi.org/10.1016/j.chemphys.2018.01.023
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Liu, Xinguo, Xie, Changjian, and Guo, Hua. Fri . "A new potential energy surface and state-to-state quantum dynamics of the $\mathrm{Li + HF → H + LiF}$ reaction". United States. https://doi.org/10.1016/j.chemphys.2018.01.023. https://www.osti.gov/servlets/purl/1538098.
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@article{osti_1538098,
title = {A new potential energy surface and state-to-state quantum dynamics of the $\mathrm{Li + HF → H + LiF}$ reaction},
author = {Liu, Xinguo and Xie, Changjian and Guo, Hua},
abstractNote = {A new global potential energy surface (PES) for the ground ($\tilde{X}^2A'$) state of the Li + HF → LiF + H reactive system is constructed by fitting 12,399 points computed at the UCCSD(T)-F12b/aug-cc-pV5Z level of theory. The use of a neural network method helps to achieve a high-fidelity fit with a root mean square error of 0.88 meV. Quantum dynamics calculations with full Coriolis coupling on the new PES yield both differential and integral cross sections over a range of energy. In agreement with experiment, the product angular distribution depends sensitively on collision energy, but all with a forward bias. Moderate internal excitation is found in the LiF product. The energy dependence of the integral cross section is in reasonably good accord with the experimental excitation function, although some quantitative differences persist. This late-barrier reaction shows a dramatic vibrational enhancement of reactivity. The mode specificity is rationalized using the Sudden Vector Projection model.},
doi = {10.1016/j.chemphys.2018.01.023},
journal = {Chemical Physics},
number = C,
volume = 509,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2018},
month = {Fri Feb 02 00:00:00 EST 2018}
}
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