气候变化领域集成服务门户(CCPortal): First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air

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DOI	10.1029/2020GL089999
	First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air
	Hellmann R.; Harvey A.H.
发表日期	2020
ISSN	0094-8276
卷号	47 期号:18
英文摘要	Kinetic isotope fractionation between water vapor and liquid water or ice depends on the ratio of the diffusivities of the isotopic species in air, but there is disagreement as to the values of these ratios and limited information about their temperature dependence. We use state-of-the-art intermolecular potential-energy surfaces for the water-nitrogen and water-oxygen pairs, along with the kinetic theory of molecular gases, to calculate from first principles the diffusivities of water isotopologues in air. The method has sufficient precision to produce accurate diffusivity ratios. For the HDO/H2O ratio, we find that the often used hard-sphere kinetic theory is significantly in error and confirm the 1978 experimental result of Merlivat. For the ratios involving 17O and 18O, the simple kinetic theory is relatively close to our more rigorous results. We provide diffusivity ratios from 190 K to 500 K, greatly expanding the range of temperatures for which these ratios are available. © 2020. The Authors.
英文关键词	Distillation; Isotopes; Kinetic theory; Kinetics; Molecular oxygen; Potential energy; Quantum chemistry; Temperature distribution; Diffusivity ratio; First principles; Intermolecular potential energy surfaces; Isotopic species; Kinetic isotope fractionation; Limited information; Temperature dependence; Water isotopologues; Diffusion; diffusion; experimental study; isotopic fractionation; nitrogen isotope; oxygen isotope; reaction kinetics; water vapor
语种	英语
来源期刊	Geophysical Research Letters
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/169696
作者单位	Institut für Thermodynamik, Helmut-Schmidt-Universität / Universität der Bundeswehr Hamburg, Hamburg, Germany; Applied Chemicals and Materials Division, National Institute of Standards and Technology, Boulder, CO, United States
推荐引用方式 GB/T 7714	Hellmann R.,Harvey A.H.. First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air[J],2020,47(18).
APA	Hellmann R.,&Harvey A.H..(2020).First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air.Geophysical Research Letters,47(18).
MLA	Hellmann R.,et al."First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air".Geophysical Research Letters 47.18(2020).