赝势
耦合簇
相对论量子化学
电子相关
原子物理学
化学
全配置交互
电离能
电离
多重态
组态交互作用
价(化学)
物理
电子
谱线
量子力学
离子
激发态
分子
作者
Detlev Figgen,Kirk A. Peterson,Michael Dolg,Hermann Stoll
摘要
New relativistic energy-consistent pseudopotentials have been generated for the 5d transition metals Hf–Pt. The adjustment was done in numerical two-component multiconfiguration Hartree–Fock calculations, using atomic valence-energy spectra from four-component multiconfiguration Dirac–Hartree–Fock calculations as reference data. The resulting two-component pseudopotentials replace the [Kr]4d104f14 cores of the 5d transition metals and can easily be split into a scalar-relativistic and a spin-orbit part. They reproduce the all-electron reference energy data with deviations of ∼0.01 eV for configurational averages and ∼0.05 eV for individual relativistic states. Full series of correlation consistent basis sets from double to quintuple-zeta have also been developed in this work for use with the new pseudopotentials. In addition, all-electron triple-zeta quality correlation consistent basis sets are also reported in order to provide calibration for the pseudopotential treatment. The accuracy of both the pseudopotentials and basis sets are assessed in extensive coupled cluster benchmark calculations of atomic ionization potentials, electron affinities, and selected excitation energies of all the 5d metal atoms, including the effects of spin-orbit coupling.
科研通智能强力驱动
Strongly Powered by AbleSci AI