Ab initio energy-adjusted pseudopotentials for the noble gases Ne through Xe: Calculation of atomic dipole and quadrupole polarizabilities

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Abstract
Nonrelativistic and one‐component relativistic energy‐adjusted ab initio pseudopotentials for the noble gases neon through xenon are presented together with corresponding optimized valence basis sets. To account for nonscalar relativistic effects the relativistic pseudopotentials are supplemented with effective spin–orbit potentials. The reliability of the presented pseudopotentials is demonstrated in atomic test calculations on ionization potentials and spin–orbit splittings in comparison with nonrelativistic and relativistic all‐electron calculations as well as experimental data. Together with extended valence basis sets the pseudopotentials are applied in calculations on the static dipole and quadrupolepolarizabilities of the noble gas atoms. The best values, computed at the coupled‐cluster level of theory [CCSD(T)], for the dipole and quadrupolepolarizabilities of the noble gases are 2.69a 3 0 and 7.52a 5 0 for Ne, 11.07a 3 0 and 52.25a 5 0 for Ar, 17.06a 3 0 and 97.39a 5 0 for Kr, and 27.66a 3 0 and 209.85a 5 0 for Xe.