Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University Auckland, Private Bag 102904, North Shore City, 0745 Auckland, New Zealand.
J Chem Phys. 2012 Jan 21;136(3):034504. doi: 10.1063/1.3675833.
A comprehensive density functional study of the group 12 chalcogenides has been carried out to study the impact of relativistic effects on the solid-state and electronic structure of the mercury chalcogenides in order to explain their unique behavior compared to the lighter group 12 congeners. For this, we present scalar-relativistic and nonrelativistic density functional calculations for several crystal structures commonly occurring in ZnX, CdX, and HgX (X = S, Se, and Te). The cohesive energies and other ground-state properties (at the zero-temperature limit) are obtained to identify the low-pressure phases and to discuss relativistic effects. Relativistic crucially influences the crystal structure in HgS, an effect less pronounced in the heavier chalcogenides HgSe and HgTe. However, for HgSe and HgTe we find that relativistic effects have a major impact on the electronic structure, where the change upon neglect of relativity goes as far as to the restoration of semiconducting properties.
我们对第 12 族的硫属元素进行了全面的密度泛函研究，以研究相对论效应对汞的硫属化物的固态和电子结构的影响，从而解释它们与较轻的第 12 族同系物相比的独特行为。为此，我们针对 ZnX、CdX 和 HgX（X = S、Se 和 Te）中几种常见晶体结构进行了标量相对论和非相对论密度泛函计算。我们获得了结合能和其他基态性质（在零温极限下），以确定低压相并讨论相对论效应。相对论对 HgS 的晶体结构有至关重要的影响，而对较重的硫属化物 HgSe 和 HgTe 的影响则不那么明显。然而，对于 HgSe 和 HgTe，我们发现相对论效应对电子结构有重大影响，忽略相对论的影响甚至会恢复半导体性质。
