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Kohn–Sham description of equilibria and charge transfer in reactive systems
Author(s) -
Nalewajski Roman F.
Publication year - 1998
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/(sici)1097-461x(1998)69:4<591::aid-qua17>3.0.co;2-2
Subject(s) - charge (physics) , chemistry , relaxation (psychology) , matrix (chemical analysis) , transfer (computing) , transfer matrix , thermodynamics , computational chemistry , state (computer science) , resolution (logic) , statistical physics , atomic physics , molecular physics , physics , quantum mechanics , algorithm , mathematics , computer science , parallel computing , psychology , social psychology , chromatography , artificial intelligence , computer vision
The pure‐ and mixed‐state descriptions of the charge transfer (CT) between complementary molecular subsystems are compared at the two‐ and three‐state approximation levels. The CT chemical potential and hardness derivatives of the resulting energy expressions are discussed. The Kohn–Sham approach to the equilibria in such mutually closed, interacting subsystems is presented and specific algorithms for calculating the hardness matrix and Fukui functions (FF) in the reactant resolution are presented. The orbital relaxation accompanying populational displacements on subsystems is examined in a more detail and the in situ FF are expressed in terms of the FF matrix of reactants. The hardness matrix equalization rule is derived. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 591–605, 1998