Jerabek Paul, Smits Odile R, Mewes Jan-Michael, Peterson Kirk A, Schwerdtfeger Peter
Department for Molecular Theory and Spectroscopy , Max-Planck-Institut für Kohlenforschung (KOFO) , Kaiser-Wilhelm-Platz 1 , D-45470 Mülheim an der Ruhr , Germany.
Centre for Theoretical Chemistry and Physics , The New Zealand Institute for Advanced Study, Massey University Auckland , Private Bag 102904, 0632 Auckland , New Zealand.
J Phys Chem A. 2019 May 16;123(19):4201-4211. doi: 10.1021/acs.jpca.9b01947. Epub 2019 May 6.
Many-body potentials up to fourth order are constructed using nonrelativistic, scalar-relativistic, and relativistic coupled-cluster theory to accurately describe the interaction between superheavy oganesson atoms. The obtained distance-dependent energy values were fitted to extended two-body Lennard-Jones and three-body Axilrod-Teller-Muto potentials, with the fourth-order term treated through a classical long-range Drude dipole interaction model. From these interaction potentials, spectroscopic constants for the oganesson dimer and solid-state properties were obtained. Furthermore, these high-level results are compared to scalar-relativistic and two-component plane-wave DFT calculations based on a tailor-made projector augmented wave pseudopotential (PAW-PP) and newly derived parameters for Grimme's dispersion correction. It is shown that the functionals PBE-D3(BJ), PBEsol, and in particular SCAN provide excellent agreement with the many-body reference for solid oganesson. Finally, the results for oganesson are compared and related to the lighter rare gas elements, and periodic trends are discussed.
利用非相对论、标量相对论和相对论耦合簇理论构建了高达四阶的多体势，以精确描述超重气奥加涅森原子之间的相互作用。将得到的距离相关能量值拟合到扩展的两体 Lennard-Jones 势和三体 Axilrod-Teller-Muto 势，其中四阶项通过经典的长程德鲁德偶极相互作用模型处理。从这些相互作用势中，得到了奥加涅森二聚体的光谱常数和固态性质。此外，将这些高水平结果与基于特制投影增强波赝势（PAW-PP）和新推导的 Grimme 色散校正参数的标量相对论和二分量平面波 DFT 计算结果进行了比较。结果表明，泛函 PBE-D3(BJ)、PBEsol，特别是 SCAN 与固态奥加涅森的多体参考结果具有极好的一致性。最后，将奥加涅森的结果与较轻的稀有气体元素进行了比较和关联，并讨论了周期趋势。
