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Charge response criteria of chemical reactivity: Fukui function indices and populational reference frames reflecting the interreactant charge coupling
Author(s) -
Nalewajski Roman F.
Publication year - 1997
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(1997)61:2<181::aid-qua1>3.0.co;2-s
Subject(s) - chemistry , diagonal , charge (physics) , chemical physics , superposition principle , computational chemistry , reactivity (psychology) , thermodynamics , molecular physics , quantum mechanics , physics , medicine , geometry , mathematics , alternative medicine , pathology
The charge response quantities of the Lewis acid (A)‐basis (B) reactants, reflecting their actual interaction in A‐B, are recommended as tools for diagnosing trends in chemical reactivity. These truly two‐reactant quantities preserve the memory of the reaction stimulus generated by the presence of the other reactant and are mainly localized in the reaction region. The Fukui function indices (FFI) of separated and interacting reactants are resolved into the pure charge transfer (CT) and CT‐induced polarization (P) components, respectively, and a role of the reactant charge relaxations, accompanying the primary charge displacements on the reaction partner ???s investigated in more detail. The associated reactant off‐diagonal responses are included in the resultant in situ FFI, in addition to the usual reactant diagonal contributions. The new collective populational reference frames reflecting the mutual interaction between reactants are introduced and used to describe the FFI of open and closed (isoelectronic) A‐B systems. They include the relaxed normal modes of the reactants, externally decoupled modes from the maximum overlap criterion, and the interreactant coupling modes. Their use in describing the open‐and closed‐system responses in systems consisting of large reactants is tested by illustrative applications to model chemisorption systems: toluene‐[V 2 O 5 ] and water‐[(110)‐rutile]. The interaction‐shaped responses are shown to reflect the chemistry of these surface complexes much better than the corresponding separated reactant quantities; the interaction‐dependent coordinate systems are shown to give rise to the most compact description of the relevant CT processes. © 1997 John Wiley & Sons, Inc.