Institute for Theoretical Chemistry, University of Cologne, Greinstr. 4, 50939 Cologne, Germany.
J Chem Phys. 2013 May 7;138(17):174113. doi: 10.1063/1.4803148.
Relativistic energy-consistent pseudopotentials for the superheavy elements with nuclear charges 119 and 120 replacing 92 electrons of a [Xe]4f(14)5d(10)5f(14) core were adjusted to relativistic multi-configuration Dirac-Coulomb-Breit finite nucleus all-electron reference data including lowest-order quantum electrodynamic effects, i.e., vacuum polarization and electron self-energy. The parameters were fitted by two-component multi-configuration Hartree-Fock calculations in the intermediate coupling scheme to the total valence energies of 131 to 140 relativistic states arising from 31 to 33 nonrelativistic configurations covering also anionic and highly ionized states, with mean absolute errors for the nonrelativistic configurations below 0.01 eV. Primitive basis sets for one- and two-component calculations with errors below 0.02 and 0.03 eV to the Hartree-Fock limit, respectively, as well as general contractions of these basis sets with double- to quadruple-zeta quality were obtained. Atomic highly correlated test calculations using the Fock-space coupled-cluster method yield for valence excitation energies and ionization potentials mean absolute errors of 26 cm(-1) and 59 cm(-1), respectively. Correlated and uncorrelated molecular test calculations show deficiencies below 0.005 Å for the bond lengths and 3 N m(-1) for the force constants.
相对论能量一致赝势用于取代 [Xe]4f(14)5d(10)5f(14) 核芯的 92 个电子的超重元素 119 和 120，调整为包括最低阶量子电动力学效应（即真空极化和电子自能）的相对论多组态 Dirac-Coulomb-Breit 有限核全电子参考数据。参数通过中间耦合方案的两分量多组态哈特ree-fock 计算进行拟合，以获得 31 到 33 个非相对论构型产生的 131 到 140 个相对论态的总价电子能量，也包括阴离子和高度电离态，非相对论构型的平均绝对误差低于 0.01 eV。对于单分量和双分量计算，获得了误差低于 0.02 和 0.03 eV 的原始基组，分别达到哈特ree-fock 极限，以及这些基组的双至四倍 zeta 质量的一般收缩。使用 Fock 空间耦合簇方法进行的原子高相关测试计算，对价激发能和电离势的平均绝对误差分别为 26 cm(-1)和 59 cm(-1)。相关和非相关分子测试计算显示，键长的误差低于 0.005 Å，力常数的误差低于 3 N m(-1)。
