Third-order Douglas–Kroll ab initio model potential for actinide elements

Abstract

Articles you may be interested inModel core potentials of p-block elements generated considering the Douglas-Kroll relativistic effects, suitable for accurate spin-orbit coupling calculations Correlated ab initio calculations of spectroscopic parameters of SnO within the framework of the higher-order generalized Douglas-Kroll transformation Accurate relativistic Gaussian basis sets determined by the third-order Douglas-Kroll approximation with a finitenucleus model Erratum: "Ab initio relativistic effective potentials with spin-orbit operators. VII. Am through element 118" [J.A relativistic ab initio model potential ͑AIMP͒ method with the third-order Douglas-Kroll ͑DK3͒ approximation has been developed for the whole series of the actinide elements from Th to Lr. Two different cores, i.e., ͓Xe, 4 f ,5d] and ͓Xe, 4 f ], have been employed and the corresponding valence basis sets, (14s10p11d9 f )/͓6s5 p5d4 f ͔ and (14s10p12d9 f )/͓6s5 p6d4 f ͔, are presented for all actinides. The mean absolute errors of the AIMP relative to the all-electron results for the atomic SCF valence orbital energies ͑⑀͒ and the radial expectation values (͗r͘) are 0.003 ͑0.001͒ hartree and 0.004 ͑0.006͒ bohr with the small ͑large͒ core set. The spectroscopic properties of the 1 ⌺ ϩ ground state of thorium monoxide, ThO, are calculated at the SCF and complete active space SCF levels. The DK3-AIMP results again satisfactorily reproduce the all-electron DK3 results. The large core set gives almost the same results as the small set for atomic and molecular calculations, suggesting that the 5d electrons can safely be omitted from the valence electrons in actinide chemistry.

The Pseudopotential Approximation in Electronic Structure Theory

“…As a result, relativistic operators, such as the scalar Douglas-Kroll operator, acting in the close proximity of the nucleus, can be applied directly to such pseudo-valence orbitals. [25] Spin-orbit effects can be included as well.…”

Search for the electric dipole moment of the electron with thorium monoxide

“…This scheme allows for efficient rejection of scattered light from the detection laser, since the emitted fluorescence photons are at a much bluer wavelength than the laser. The spectroscopy of the ThO molecule has been extensively studied by previous workers [15][16][17][18][19][20]. As well as having spectroscopic constants that are precisely known for a number of electronic states, a significant experimental advantage of this system is provided by the fact that all the relevant transitions-for optical pumping, state-preparation and detection-are accessible with readily available laser diodes.…”

Electron correlation and relativistic effects in atomic structure calculations of the thorium atom

“…order Douglas-Kroll approximation has been developed from Th to Lr by Paulovič et al 11 Roos et al 5,12,13 have computed some low-lying spin-orbit states and the first ionization energy of the Th atom at CASPT2/CAS-SO level using AIMP method, whereas Tyagi 14 has calculated the first ionization energy using higher level non-spin-orbit CI calculation with cc-pVDZ basis set.…”