Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4-x2- Species in the Aqueous Phase by the ONIOM Method | |
He, Yuyang4,5; Gao, Caihong1; Wei, Wei2; Liu, Yun1,3 | |
通讯作者 | He, Yuyang(yhe@mail.iggcas.ac.cn) |
发表期刊 | ACS EARTH AND SPACE CHEMISTRY |
2023-01-19 | |
卷号 | 7期号:1页码:142-155 |
ISSN | 2472-3452 |
摘要 | Molybdenum (Mo) is a redox-sensitive metal element. Its isotope composition (delta Mo-98) has the potential to reconstruct oceanic oxygenation extent in deep time. To accurately reconstruct the bulk delta Mo-98 value of ancient seawater from sediment records, it is necessary to clarify the Mo isotope fractionation mechanism during the transformation among thiomolybdates (MoOxS4-x2-, x = 0 similar to 4) in marine environments. For aqueous systems, predicting the equilibrium isotope fractionation factors theoretically needs careful treatment of solvent effects. The commonly used water-droplet or periodical boundary condition methods are not only troublesome but also time-consuming. We test the efficiency of the two-layer own N-layer integrated molecular orbital molecular mechanics (ONIOM) method in predicting the reduced partition function ratios (beta factors) of the MoOxS42- species in aqueous phases. Compared to other methods, the ONIOM method can produce beta factors with the same accuracy and considerably fewer computational resources. The predicted beta factors are in the order MoO4(aq)2- > MoO3S(aq)2- > MoO2S2(aq)2- > MoOS3(aq)2- > MoS4(aq)2-, which are in line with previous laboratory experiments and field observations. The new results provide the basic data for reconstructing delta Mo-98 values in suboxic, ferruginous, and weakly euxinic sediments. |
关键词 | paleoredox proxy ab initio molecular dynamics implicit solvent model dispersion correction water-droplet periodical boundary condition |
DOI | 10.1021/acsearthspacechem.2c00268 |
收录类别 | SCI |
语种 | 英语 |
WOS记录号 | WOS:001111265000004 |
关键词[WOS] | INITIO MOLECULAR-DYNAMICS ; EFFECTIVE CORE POTENTIALS ; CARBONATE MINERALS ; EUXINIC SEDIMENTS ; GAUSSIAN-ORBITALS ; MODERN BLACK ; MOLYBDENUM ; OXYGEN ; ADSORPTION ; MECHANISM |
WOS研究方向 | Chemistry ; Geochemistry & Geophysics |
WOS类目 | Chemistry, Multidisciplinary ; Geochemistry & Geophysics |
资助项目 | National Science Foundation of China (NSFC)[4217030170] ; National Science Foundation of China (NSFC)[42150202] ; NSFC[41903019] ; NSFC[42130114] ; CAS[XDB41000000] ; NSFC project[41902025] ; Civil Aerospace Technologies of China National Space Administration[D020203] |
项目资助者 | National Science Foundation of China (NSFC) ; NSFC ; CAS ; NSFC project ; Civil Aerospace Technologies of China National Space Administration |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://dspace.imech.ac.cn/handle/311007/93623 |
专题 | 高温气体动力学国家重点实验室 |
通讯作者 | He, Yuyang |
作者单位 | 1.Chinese Acad Sci, Inst Geochem, State Key Lab Ore Deposit Geochem, Guiyang 550081, Guizhou, Peoples R China 2.Univ Sci & Technol China, Sch Earth & Space Sci, CAS Key Lab Crust Mantle Mat & Environm, Hefei 230026, Anhui, Peoples R China 3.Chengdu Univ Technol, Coll Earth Sci, Int Ctr Planetary Sci, Chengdu 610059, Sichuan, Peoples R China 4.Chinese Acad Sci, Inst Geol & Geophys, Key Lab Earth & Planetary Phys, Beijing 100029, Peoples R China 5.Chinese Acad Sci, Inst Mech, State Key Lab High Temp Gas Dynam, Beijing 100190, Peoples R China |
推荐引用方式 GB/T 7714 | He, Yuyang,Gao, Caihong,Wei, Wei,et al. Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4-x2- Species in the Aqueous Phase by the ONIOM Method[J]. ACS EARTH AND SPACE CHEMISTRY,2023,7,1,:142-155. |
APA | He, Yuyang,Gao, Caihong,Wei, Wei,&Liu, Yun.(2023).Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4-x2- Species in the Aqueous Phase by the ONIOM Method.ACS EARTH AND SPACE CHEMISTRY,7(1),142-155. |
MLA | He, Yuyang,et al."Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4-x2- Species in the Aqueous Phase by the ONIOM Method".ACS EARTH AND SPACE CHEMISTRY 7.1(2023):142-155. |
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