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Charge sensitivities of the externally interacting open reactants
Author(s) -
Nalewajski Roman F.
Publication year - 2000
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(2000)78:3<168::aid-qua4>3.0.co;2-j
Subject(s) - chemistry , catalysis , fukui function , chemical physics , decoupling (probability) , matrix (chemical analysis) , acceptor , adsorption , computational chemistry , organic chemistry , quantum mechanics , physics , electrophile , chromatography , control engineering , engineering
Effective chemical potential, hardness, softness, and Fukui function quantities of the simultaneously open reactants , e.g., adsorbates in catalytic systems, are examined. The derived reduced expressions in terms of the canonical chemical potentials and condensed hardness matrix elements of such molecular subsystems are compared with the corresponding analogs for the case of the closed complementary subsystem. Implications of the catalyst‐induced changes in the condensed hardness matrix of the reactive system consisting of a pair of donor/acceptor adsorbates, in the preferred complementary arrangement with the acidic/basic active sites of the surface, respectively, are discussed and interpreted as manifestations of the Le Châtelier–Braun principle. Only in such a complementary arrangement is the in‐phase , concerted, mutually enhancing pattern of the polarizational and charge transfer flows of electrons in a catalytic system obtained. The activating influence of the catalyst is identified through its softening, decoupling effect on the adsorbates. The catalyst‐induced chemical potential equalization creates electronic instability in the system of adsorbed species, thus increasing their reactivity. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 78: 168–178, 2000