摘要
To investigate equilibrium mercury(Hg)and lead(Pb)isotope fractionation caused by the nuclear volume effect(NVE)in crystals,the electron densities at nuclei(i.e.,|Ψ(0)|2)for Hg-or Pb-bearing crystalline compounds were investigated by using the relativistic spin orbit zeroth-order regular approximation(ZORA)method with a three-dimensional periodic boundary condition based on the density functional theory(DFT).Many isotope fractionation factors of crystalline compounds are provided for the first time.Our results show,even at1000℃,NVE-driven Hg and Pb isotope fractionation are meaningfully large,i.e.,range from 0.12‰to 0.49‰(202Hg/^(198)Hg),from-0.20‰to 0.17‰(208Pb/^(206)Pb)and from-0.08‰to 0.06‰(207Pb/^(206) Pb)relative to Hg0 vapor and Pb0 vapor,respectively.Specifically,the fractionations range from-0.06‰to-0.20‰(208Pb/^(206)Pb)and from-0.02‰to-0.08‰(207Pb/^(206)Pb)for Pb2+-bearing species,from 0.10‰to 0.17‰(208Pb/^(206)Pb)and from 0.04‰to 0.06‰(207Pb/^(206)Pb)for Pb4+-bearing species in crystals.All calculated Hg-bearing species in crystals will enrich heavier isotope(202Hg)relative to Hg0 vapor.Meanwhile,Pb4+-bearing species enrich heavier Pb isotopes(208Pb and 207Pb)than Pb^(2+)-bearing species in crystals,which the enrichment can be up to 0.37‰(208-Pb/^(206)Pb)and 0.14‰(207Pb/^(206)Pb)at 1000℃,due to their NVEs are in opposite directions.The NVE-driven MIFs of Hg isotopes,which are compared to the Hg202-Hg198baseline,are up to-0.158‰(ΔNV199Hg),-0.024‰(ΔNV200Hg)and-0.094‰(ΔNV201Hg)relative to Hg0 vapor at5000 C.For all studied Hg-bearing species in crystals,the MIFs of two odd-mass isotopes(i.e.,ΔNV199Hg andΔNV201Hg)will be changed proportionally and their ratio(i.e.,ΔNV199Hg/ΔNV201Hg)will be a constant 1.67.The NVE can also cause mass-independent fractionations for 207Pb and 204 Pb compared to the baseline of 208Pb and 206Pb.The largest NVEdriven MIFs are 0.043‰(ΔNV207Pb)and-0.040‰(ΔNV204Pb)among all the studied species relative to Pb0 vapor at 5000 C.The magnitudes of odd-mass isotope MIF(ΔNV207Pb)and even-mass isotope MIF(ΔNV204Pb)are almost the same but with opposite signs,leading to the MIF ratio of them(i.e.,ΔNV207Pb/ΔNV204Pb)is-1.08.
基金
supported by National Natural Science Foundation of China (NSFC) projects (41703012)
Qinghai Science and Technology projects (2018-ZJ-956Q)
the supports of the Strategic Priority Research Program (B) of CAS (XDB18010100, XDB41000000)
pre-research Project on Civil Aerospace Technologies No. D020202 funded by the Chinese National Space Administration
NSFC projects (41530210)。
作者简介
Yun Liu,Liuyun@vip.gyig.ac.cn。
