Ab initio calculation of energy levels of trivalent lanthanide ions

Physical Chemistry Chemical Physics : PCCP
Alexandra Ya FreidzonVitaliy I Vovna

Abstract

The energy levels of Ln3+ ions are known to be only slightly dependent on the ion environment. This allows one to predict the spectra of f-f transitions in Ln3+ complexes using group theory and simple semiempirical models: Russell-Saunders scheme for spin-orbit coupling, ligand-field theory for the splitting of the electronic levels, and Judd-Ofelt parameterization for reproducing the intensity of f-f transitions. Nevertheless, a fully ab initio computational scheme employing no empirical parameterization and suitable for any asymmetrical environment of Ln3+ would be instructive. Here we present such a scheme based on the multireference SA-CASSCF/XMCQPDT2/SO-CASSCF (state-averaged complete active space SCF, quasi-degenerate perturbation theory, and spin-orbit CASSCF) approach for trivalent lanthanide ions from Ce3+ (4f1) to Yb3+ (4f13). To achieve the most accurate results, we analyse the factors that influence the accuracy of the calculation: basis set size, state averaging scheme, effect of the low-spin states on the energy gap between the high-spin states (e.g., effect of triplets on the septet-quintet gaps in f6 or f8 configurations), and radial and angular correlations in the 4f shell. Our calculated energy levels agree we...Continue Reading

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Citations

Oct 12, 2019·Physical Chemistry Chemical Physics : PCCP·Dayton J VogelJessica M Rimsza
Mar 6, 2019·Inorganic Chemistry·David Esteban-GómezCarlos Platas-Iglesias
Jan 25, 2020·The Journal of Physical Chemistry. a·Aurora Rodríguez-RodríguezCarlos Platas-Iglesias
Jul 3, 2020·Inorganic Chemistry·Christopher M KotykLinda H Doerrer
Nov 19, 2021·Journal of Chemical Theory and Computation·Rulin FengJochen Autschbach

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Software Mentioned

MRSOCI
XMCQDPT2
US
MCQDPT
GAMESS
CASPT2
Firefly

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