Static and Frequency‐Dependent Dipole–Dipole Polarizabilities of All Closed‐Shell Atoms up to Radium: A Four‐Component Relativistic DFT Study |
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Authors: | Radovan Bast Dr Andreas Heßelmann Dr Pawe? Sa?ek Dr Trygve Helgaker Prof Dr Trond Saue Dr |
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Institution: | 1. Institut de Chimie, UMR 7177 CNRS/Université Louis Pasteur, Laboratoire de Chemie Quantique, 4 Rue Blaise Pascal, 67000 Strasbourg, France, Fax: (+33)?390241589;2. Lehrstuhl für Theoretische Chemie, Universit?t Erlangen‐Nürnberg, 91058 Erlangen, Germany;3. Laboratory of Theoretical Chemistry, The Royal Institute of Technology, 10691 Stockholm, Sweden;4. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo, Norway |
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Abstract: | We test the performance of four‐component relativistic density functional theory by calculating the static and frequency‐dependent electric dipole–dipole polarizabilities of all (ground‐state) closed‐shell atoms up to Ra. We consider 12 nonrelativistic functionals, including three asymptotically shape‐corrected functionals, by using two smooth interpolation schemes introduced by the Baerends group: the gradient‐regulated asymptotic connection (GRAC) procedure and the statistical averaging of (model) orbital potentials (SAOP). Basis sets of doubly augmented triple‐zeta quality are used. The results are compared to experimental data or to accurate ab initio results. The reference static electric dipole polarizability of palladium has been obtained by finite‐field calculations using the coupled‐cluster singles, doubles, and perturbative triples method within this work. The best overall performance is obtained using hybrid functionals and their GRAC shape‐corrected versions. The performance of SAOP is among the best for nonhybrid functionals for Group 18 atoms but its precision degrades when considering the full set of atoms. In general, we find that conclusions based on results obtained for the rare‐gas atoms are not necessarily representative of the complete set of atoms. GRAC cannot be used with effective core potentials since the asymptotic correction is switched on in the core region. |
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Keywords: | ab initio calculations closed‐shell atoms density functional calculations polarizability quantum chemistry |
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