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Basis set quality versus size II. Approximate GTO wave functions for second row transition metal atoms
Author(s) -
Faegri Knut,
Biran Gil
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.540100407
Subject(s) - basis set , wave function , basis (linear algebra) , atomic orbital , sto ng basis sets , atomic physics , basis function , mathematics , excitation , hartree–fock method , quality (philosophy) , quantum mechanics , physics , chemistry , mathematical analysis , geometry , linear combination of atomic orbitals , molecule , electron
Basis sets ranging in size from (16, 10, 7) to (20, 14, 11) have been derived for the atoms Y–Cd. Separate sets represent the energy optimized wave functions for each of the s 2 d n , s 1 d n+1 , and s 0 d n+2 configurations. The energies from the largest sets are within 3 mhartrees of the values obtained in numerical Hartree–Fock calculations. Reasonable Hartree–Fock s 2 d n – s 1 d n+1 and s 2 d n – s 0 d n+2 excitation energies may be obtained either using the largest basis sets, or using d ‐orbitals optimized for the s 0 d n+2 configurations. The basis sets are slightly unbalanced in favor of the s ‐functions and in disfavor of the d ‐functions, but various alternative basis sets may be derived by combining parts of the five parent sets. The convergence of radial expectation values is discussed.