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Improved SCF interaction energy decomposition scheme corrected for basis set superposition effect
Author(s) -
Sokalski W. A.,
Roszak S.,
Hariharan P. C.,
Kaufman Joyce J.
Publication year - 1983
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.560230308
Subject(s) - counterpoise , interaction energy , superposition principle , basis set , basis (linear algebra) , decomposition , charge exchange , energy (signal processing) , charge (physics) , chemistry , scheme (mathematics) , set (abstract data type) , dimer , computational chemistry , statistical physics , physics , quantum mechanics , computer science , mathematics , molecule , density functional theory , mathematical analysis , geometry , organic chemistry , programming language , ion
A modified scheme for SCF interaction energy decomposition has been proposed where the nonphysical basis set superposition error ( BSSE ) has been corrected by means of the counterpoise method. A new procedure to separate the exchange and induction energy terms free of nonphysical BSSE has been tested in the case of the H 2 O dimer. The first order BSSE appears to be non‐negligible for strong hydrogen bonded complexes. In addition the scheme allows separation of the long‐controversial charge‐transfer contribution within the induction term, which has been considerably overestimated in previous studies.