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Gaussian orbitals optimized for lower bounds of hydrogenic atoms
Author(s) -
Johnson J. W.,
Poshusta R. D.
Publication year - 1973
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560070510
Subject(s) - atomic orbital , slater type orbital , sto ng basis sets , gaussian , linear combination of atomic orbitals , eigenvalues and eigenvectors , atom (system on chip) , molecular orbital , atomic physics , wave function , molecular orbital theory , physics , mathematics , quantum mechanics , chemistry , molecule , computer science , embedded system , electron
Various optimization criteria are compared for the hydrogen atom to find orbitals which improve lower bounds computed from the Weinstein, Temple, and Stevenson‐Crawford formulas. Minimization of squared energy deviation, “variance,” is recommended because the resulting lower bound orbitals give excellent lower bounds, converge to the exact wave function, are relatively easy to optimize, and are insensitive to the estimated energy eigenvalue. New linear combinations of Gaussian orbitals which minimize the variance are presented for the 1 s , 2 s , 2 p , 3 s , 3 p , and 3 d orbitals. These orbitals are compared with previous linear combinations with regard to their expectation values and local properties.