Ab initio relativistic effective potentials with spin‐orbit operators. VI. Fr through Pu

Abstract

Ab initio averaged relativistic effective core potentials (AREP), spin-orbit (so) operators, and valence basis sets are reported for the elements Fr through Pu in the form of expansions in Gaussian-type functions. Gaussian basis sets with expansion coefficients for the low-energy states of each atom are given. Atomic orbital energies calculated under the j -j coupling scheme within the self-consistent field approximation and employing the AREP'S in their unaveraged form (REP'S) agree to within 10% of orbital energies due to numerical all-electron Dirac-Fock calculations. The accuracy of the AREP'S and so operators is also shown to be good through comparisons of calculated so splitting energies with all-electron Dirac-Fock results.

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

“…Sets paired to PPs are restricted to the CRENBL set of Christiansen and co-workers 17 and the roughly quadruple-zeta quality ECP78MDF set of Lim et al 18,19 For all-electron calculations, the atomic natural orbital (ANO) basis sets of Roos and co-workers, 20 denoted ANO-RCC, the Dirac-Coulomb relativistic correlation consistent sets of Dyall, 21 and the Sapporo natural orbital based segmented contracted Gaussian (NOSeC) sets of Noro et al are available in a range of sizes from DZ to QZ. 22 The former are designed for use with the second-order Douglas-Kroll-Hess (DKH) Hamiltonian and the latter for third-order DKH.…”

The ab initio model potential method: Lanthanide and actinide elements

“…͑For these elements, several sets of relativistic pseudopotentials are available in the literature. [16][17][18][19][20] ͒ We present ͓Kr,4d͔ core AIMPs together with 5s,5p,4f ,5d,6s optimized valence basis sets and Wood-Boring spin-orbit operators for Ce-Lu, and ͓Xe,4f ,5d͔ core AIMPs with 6s,6p,5f ,6d,7s optimized valence basis sets and Wood-Boring spin-orbit operators for Th-Lr. It is worth noticing that the Gaussian primitive functions that have been optimized here with the Cowan-Griffin relativistic Hamiltonian are expected to be transferable to relativistic AIMPs based on the Douglas-Kroll-Hess Hamiltonian, 21,22 as was the case of the transition metal elements from Sc to Hg.…”

Electronic structure of crystalline uranium nitride: LCAO DFT calculations

“…RECPCER (Christiansen, Ermler, Ross) are reported for the elements Fr through Pu in [13]. Use of the RECPCER operator in the complete form (with ESOP) requires a two-component spinor (spinorbital) formalism in molecular or crystalline calculations.…”