Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4-x2- Species in the Aqueous Phase by the ONIOM Method

doi:10.1021/acsearthspacechem.2c00268

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	Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoO_xS_4-x^2- Species in the Aqueous Phase by the ONIOM Method
	He, Yuyang 1,2; Gao, Caihong 5; Wei, Wei 4; Liu, Yun 3,5
刊名	ACS EARTH AND SPACE CHEMISTRY
	2023-01-19
卷号	7 期号:1 页码:142-155
关键词	paleoredox proxy ab initio molecular dynamics implicit solvent model dispersion correction water-droplet periodical boundary condition
ISSN号	2472-3452
DOI	10.1021/acsearthspacechem.2c00268
通讯作者	He, Yuyang(yhe@mail.iggcas.ac.cn)
英文摘要	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.
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]
WOS关键词	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
语种	英语
WOS记录号	WOS:001111265000004
资助机构	National Science Foundation of China (NSFC) ; NSFC ; CAS ; NSFC project ; Civil Aerospace Technologies of China National Space Administration
内容类型	期刊论文
源URL	[http://dspace.imech.ac.cn/handle/311007/93622]
专题	力学研究所_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 Mech, State Key Lab High Temp Gas Dynam, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Inst Geol & Geophys, Key Lab Earth & Planetary Phys, Beijing 100029, Peoples R China 3.Chengdu Univ Technol, Coll Earth Sci, Int Ctr Planetary Sci, Chengdu 610059, Sichuan, Peoples R China 4.Univ Sci & Technol China, Sch Earth & Space Sci, CAS Key Lab Crust Mantle Mat & Environm, Hefei 230026, Anhui, Peoples R China 5.Chinese Acad Sci, Inst Geochem, State Key Lab Ore Deposit Geochem, Guiyang 550081, Guizhou, 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 MoO_xS_4-x^2- 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 MoO_xS_4-x^2- 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 MoO_xS_4-x^2- Species in the Aqueous Phase by the ONIOM Method".ACS EARTH AND SPACE CHEMISTRY 7.1(2023):142-155.