Ab initio relativistic effective potentials with spin–orbit operators. V. Ce through Lu

Abstract

Ab initio averaged relativistic effective core potentials, spin–orbit operators, and valence basis sets are reported for the fourteen lanthanide elements Ce through Lu in the form of expansions in Gaussian-type functions. Gaussian basis sets with atomic orbital coefficients for low energy states of each atom are also tabulated. Hartree–Fock orbital energies calculated in conjunction with the relativistic effective core potentials using the j-j coupling scheme agree to within 10% of those due to numerical all-electron Dirac–Fock calculations. Excitation energies, ionization potentials, and spin–orbit splittings are compared to all electron, energy-adjusted effective core potential, and experimental results.

Influence of the N‐Bridging Ligand on Magnetic Relaxation in an Organometallic Dysprosium Single‐Molecule Magnet

“…Taking the spins on the two Dy centres to be parallel gives a total spin of S = 5 and a multiplicity of 11. To describe appropriately the Dy atoms we employed the large core (54 electron) CRENBL [15] relativistic effective core potential. The accompanying valence basis set, from reference [15], was fully uncontracted to the primitive set (6s 6p 6d 6f).…”

“…To describe appropriately the Dy atoms we employed the large core (54 electron) CRENBL [15] relativistic effective core potential. The accompanying valence basis set, from reference [15], was fully uncontracted to the primitive set (6s 6p 6d 6f). All other atoms were described with the all-electron 6-31GA C H T U N G T R E N N U N G (d,p) basis, [16] and the B3LYP [17] exchange-correlation functional was used.…”

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.…”

First principle quantum description of the energetics associated with LaBr<inf>3</inf>, LaCl<inf>3</inf>, and Ce doped scintillators

“…To obtain the excited singlet and triplet energies, both single excitation configuration interaction (xCIS) HF [22] and time dependent (TD) DFT calculation were performed. Pseudo potentials employed for La and Br were based on extended core potentials (ECPs) (CRENBL [23] and SBKJC [24])while an all electron self consistent double zeta basis set (augcc-pvdz [25]) was employed for Cl. DFT ground state calculations were performed using a numerical basis set approach employed by DMOL3 [26], [27].…”