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Basis set selections for relativistic self‐consistent field calculations
Author(s) -
Lee Yoon Sup,
Baeck Kyoung Koo,
McLean A. D.
Publication year - 1989
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.540100112
Subject(s) - basis set , basis (linear algebra) , atomic orbital , sto ng basis sets , slater type orbital , component (thermodynamics) , linear combination of atomic orbitals , physics , relativistic quantum chemistry , spinor , molecular orbital , field (mathematics) , quantum mechanics , electron , mathematics , geometry , molecule , pure mathematics
Practical methods of generating reliable and economic basis sets for relativistic self‐consistent fields (RSCF) calculations are developed. Large component basis sets are generated from constrained optimizations of exponents in the nonrelativistic atomic calculations for light atoms. For heavy atoms, large component basis sets for inner core orbitals are generated by fitting numerical atomic spinors of Dirac‐Hartree‐Fock calculations with appropriate number of Slater‐type functions. Small component basis sets are obtained by using the kinetic balance condition and other computational criteria. With judicious selections of the basis sets, virtual orbitals in RSCF calculations become very similar to those in nonrelativistic calculations, implying that relativistic virtual orbitals can be used in electron correlation calculations in the same manner as the conventional nonrelativistic virtual orbitals. It is also evident that the Koopmans' theorem is also valid in RSCF results.