Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany.
J Chem Phys. 2017 Jul 7;147(1):014109. doi: 10.1063/1.4985567.
A quasi-relativistic two-component approach for an efficient calculation of P,T-odd interactions caused by a permanent electric dipole moment of the electron (eEDM) is presented. The approach uses a (two-component) complex generalized Hartree-Fock and a complex generalized Kohn-Sham scheme within the zeroth order regular approximation. In applications to select heavy-elemental polar diatomic molecular radicals, which are promising candidates for an eEDM experiment, the method is compared to relativistic four-component electron-correlation calculations and confirms values for the effective electric field acting on the unpaired electron for RaF, BaF, YbF, and HgF. The calculations show that purely relativistic effects, involving only the lower component of the Dirac bi-spinor, are well described by treating only the upper component explicitly.
本文提出了一种准相对论双分量方法，用于高效计算电子固有电偶极矩（eEDM）引起的 P,T- 奇相互作用。该方法在零阶正则近似下使用（双分量）复广义哈特ree-fock 和复广义 kohn-sham 方案。在应用于选择重元素极性双原子分子自由基时，该方法与相对论四分量电子相关计算进行了比较，并为 raf、baf、ybf 和 hgf 上未配对电子的有效电场确定了数值。计算表明，仅通过显式处理上分量，即可很好地描述仅涉及狄拉克双旋量下分量的纯相对论效应。
