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Accuracy of the electrostatic theorem for high‐quality Slater and Gaussian basis sets
Author(s) -
Fernández Rico J.,
López R.,
Ema I.,
Ramírez G.
Publication year - 2004
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.20088
Subject(s) - basis (linear algebra) , sto ng basis sets , basis set , gaussian , linear combination of atomic orbitals , feynman diagram , quality (philosophy) , statistical physics , atomic orbital , quantum mechanics , physics , computational chemistry , atomic physics , mathematics , chemistry , geometry , molecule , electron
The fulfillment of the Hellmann–Feynman electrostatic theorem is examined for the sequences of cc‐pVxZ and cc‐pCVxZ Gaussian basis sets as well as for the VBx and CVBx basis sets of Slater‐type orbitals. The difference between the energy gradient and electrostatic forces is large in small Gaussian basis sets of the two types, but decreases quickly as the basis sets improve. In VBx Slater basis sets these differences are small but the improvement is irregular, whereas in CVBx basis sets the fulfillment of the electrostatic theorem is very satisfactory. For the high‐quality basis sets (cc‐pV5Z, cc‐pCVQZ, cc‐pCV5Z, CVB2, and CVB3) the energy gradient can be replaced by the electrostatic force in most practical applications. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004