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Relativistic correlating basis sets for actinide atoms from 90 Th to 103 Lr
Author(s) -
Noro Takeshi,
Sekiya Masahiro,
Osanai You,
Koga Toshikatsu,
Matsuyama Hisashi
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20537
Subject(s) - atomic orbital , actinide , ground state , gaussian , atomic physics , relativistic quantum chemistry , chemistry , electron , physics , computational chemistry , quantum mechanics , inorganic chemistry
For 14 actinide atoms from 90 Th to 103 Lr, contracted Gaussian‐type function sets are developed for the description of correlations of the 5 f , 6 d , and 7 s electrons. Basis sets for the 6 d orbitals are also prepared, since the orbitals are important in molecular environments despite their vacancy in the ground state of some actinides. A segmented contraction scheme is employed for the compactness and efficiency. Contraction coefficients and exponents are so determined as to minimize the deviation from accurate natural orbitals of the lowest term arising from the 5 f n −1 6 d 1 7 s 2 configuration. The spin‐free relativistic effects are considered through the third‐order Douglas‐Kroll approximation. To test the present correlating sets, all‐electron calculations are performed on the ground state of 90 ThO molecule. The calculated spectroscopic constants are in excellent agreement with experimental values. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007