The theory of equilibrium isotope fractionations for gaseous molecules under super-cold conditions
Yining Zhang;Yun Liu
刊名Geochimica et Cosmochimica Acta
2018
卷号238页码:123-149
英文摘要

It is necessary to build a proper theoretical method that can precisely describe isotope fractionation processes under super-cold (<200 K) conditions, because there have been many isotopic data obtained in our solar system that are related to such processes. However, current methods of isotope fractionation calculation, i.e., the Bigeleisen-Mayer equation and its higher-order energy corrections, may not be applicable to super-cold conditions. Here, we have checked important assumptions and higher-order corrections that can affect isotope fractionations of gas-phase molecules under super-cold conditions and developed a new theoretical method for calculating equilibrium isotope fractionation factors. Compared with previous works, we have added three new corrections into our calculation, i.e., nuclear-spin weights for quantum mechanical rotation, correction for Born-Oppenheimer approximation (BOA), and inversion splitting effect for non-planar molecules such as NH3. We further examined gaseous molecules of geochemistry and cosmochemistry relevance, e.g., H-2, HF, HCl, H2O, H2S, HCHO, NH3, CH4 and their deuterated isotopologues. We found that the correction for BOA, which was rarely considered in previous studies, is important for those gaseous molecules under super-cold conditions. In case of D/H, C-13/C-12 and O-18/O-16 exchanges among organic molecules, BOA correction cannot be ignored even at ambient or higher temperature conditions. Most isotope fractionation trends at super-cold conditions reported here are quite different from their counterparts at ambient or higher temperature conditions. The method proposed here will extend our capability in interpreting equilibrium isotope fractionations to super-cold conditions in the solar system. 

语种英语
内容类型期刊论文
源URL[http://ir.gyig.ac.cn/handle/42920512-1/8852]  
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 550002, China
2.University of Chinese Academy of Sciences, Beijing 100049, China
推荐引用方式
GB/T 7714
Yining Zhang;Yun Liu. The theory of equilibrium isotope fractionations for gaseous molecules under super-cold conditions[J]. Geochimica et Cosmochimica Acta,2018,238:123-149.
APA Yining Zhang;Yun Liu.(2018).The theory of equilibrium isotope fractionations for gaseous molecules under super-cold conditions.Geochimica et Cosmochimica Acta,238,123-149.
MLA Yining Zhang;Yun Liu."The theory of equilibrium isotope fractionations for gaseous molecules under super-cold conditions".Geochimica et Cosmochimica Acta 238(2018):123-149.
个性服务
查看访问统计
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。


©版权所有 ©2017 CSpace - Powered by CSpace