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On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC)

文献类型:期刊论文

作者Yining Zhang; Yun Liu
刊名Chemical Geology
出版日期2024
卷号666页码:122303
关键词H/d Isotopes equilibrium Isotope Effects (Eies) full Partition Function Ratio (Fpfr) path Integral Monte Carlo (Pimc) super-cold Conditions theoretical Calculations
DOI10.1016/j.chemgeo.2024.122303
英文摘要

Accurate estimations of Hydrogen/Deuterium (H/D) isotope effects have been a long-standing problem since the beginning of stable isotope geochemistry, primarily due to their strong nuclear quantum effects (NQEs). Currently, the D/H ratio plays a key role in deciphering the origin and evolution of water ice and organics in the solar system. Additionally, the Big-bang origin of Deuterium necessitates that the observed D/H variations be linked to isotope exchange reactions, such as HD + H2O ↔ H2 + HDO. Therefore, an accurate benchmark dataset describing the equilibrium H/D isotope fractionations at low temperatures (≤ 200 K) is essential for interpreting rapidly accumulating astrochemical observation data. In this study, we implemented and compared two methods developed for evaluating the NQEs of H/D isotopes: 1) the Full Partition Function Ratio (FPFR) method and 2) the Path Integral Monte Carlo (PIMC) method. Both were assessed for their accuracy and efficiency in estimating equilibrium isotope effects (EIEs) using 10 common interstellar small molecules (H2, HF, HCl, HCN, HNC, H2O, H2S, NH3HCHO, and CH4) as examples. Most of them are calculated at high precision for the first time. For the FPFR method, several higher-order corrections to the Urey-Bigeleisen-Mayer model were considered, including anharmonicity, quantum mechanical rotation with nuclear-spin statistics, and corrections to the Born-Oppenheimer approximation. For the PIMC method, four different actions related to the thermal density matrix are used. These include the primitive and three fourth-order actions (Takahashi and Imada, Suzuki-Chin and Chin approximations), based on the direct scaled-coordinates transformation. Three main conclusions are obtained: 1) Under the framework of Born-Oppenheimer approximation, the PIMC method holds the same and even slightly better accuracy (more comprehensive descriptions of quantum anharmonicities) in estimating EIEs for H/D isotopes as the FPFR method. However, both methods suffer from the neglection of the DBOC when using the Born-Oppenheimer potential energy surfaces. For the PIMC method, additional corrections for particle distinguishability must be considered when nuclear spin statistics exhibit its effects at low temperatures (e.g., < 160 K for H2). 2) Among the four actions, three fourth-order actions show better convergence and efficiency (2.2 to 26.5 times speedups at 50 K) than the primitive action, making them superior candidates for PIMC simulations at super-cold (≤ 200 K) conditions. 3) A combination of accurate potential energy surface with the PIMC method serves as an alternative way for theoretical estimations of H/D isotope effects.

 

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语种英语
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专题地球化学研究所_矿床地球化学国家重点实验室
作者单位1.State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, China
2.International Center for Planetary Science, College of Earth and Planetary Sciences, Chengdu University of Technology, Chengdu 610059, China
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Yining Zhang,Yun Liu. On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC)[J]. Chemical Geology,2024,666:122303.
APA Yining Zhang,&Yun Liu.(2024).On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC).Chemical Geology,666,122303.
MLA Yining Zhang,et al."On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC)".Chemical Geology 666(2024):122303.

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来源:地球化学研究所

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