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Ring-polymer molecular dynamics studies of thermal rate coefficients for the reaction F + H2O → HF + OH
jli15
Author NameAffiliationE-mail
jli15 School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China jli15@cqu.edu.cn 
Abstract:
The prototype tetra-atomic reaction F + H2O → HF + OH plays a significant role in both atmospheric and astronomical chemistry. In this work, thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics (RPMD) method on a full-dimensional potential energy surface (PES). This PES is the most accurate one for the title reaction, as demonstrated by the correct barrier height and reaction energy, compared to the benchmark calculations by the focal point analysis (FPA) and the high accuracy extrapolated ab initio thermochemistry (HEAT) methods. The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation (SCTST/2DME) technique, and some experimental measurements. As has been found in many RPMD applications, quantum effects, including tunneling and zero-point energy effects, can be efficiently and effectively captured by the RPMD method. In addition, the convergence of the results with respect to the number of beads is rapid, which is also consistent with previous RPMD applications.
Key words:  rate coefficients, ring polymer molecular dynamics, quantum tunneling
FundProject:
Ring-polymer molecular dynamics studies of thermal rate coefficients for the reaction F + H2O → HF + OH
jli15
摘要:
The prototype tetra-atomic reaction F + H2O → HF + OH plays a significant role in both atmospheric and astronomical chemistry. In this work, thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics (RPMD) method on a full-dimensional potential energy surface (PES). This PES is the most accurate one for the title reaction, as demonstrated by the correct barrier height and reaction energy, compared to the benchmark calculations by the focal point analysis (FPA) and the high accuracy extrapolated ab initio thermochemistry (HEAT) methods. The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation (SCTST/2DME) technique, and some experimental measurements. As has been found in many RPMD applications, quantum effects, including tunneling and zero-point energy effects, can be efficiently and effectively captured by the RPMD method. In addition, the convergence of the results with respect to the number of beads is rapid, which is also consistent with previous RPMD applications.
关键词:  rate coefficients, ring polymer molecular dynamics, quantum tunneling
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