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Sensitivity analysis of charge transfer systems: In situ quantities, intersecting state model and its implications
Author(s) -
Nalewajski Roman F.
Publication year - 1994
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.560490512
Subject(s) - chemistry , fukui function , context (archaeology) , population , degrees of freedom (physics and chemistry) , charge (physics) , electron , orientation (vector space) , acceptor , ellipse , molecule , atomic physics , chemical physics , computational chemistry , thermodynamics , physics , quantum mechanics , geometry , mathematics , organic chemistry , paleontology , demography , electrophile , astronomy , sociology , biology , catalysis
The states of reactants in the donor (base, B )‐acceptor (acid, A ) systems are examined and the charge transfer (CT) in situ sensitivities, including the chemical potential, hardness, softness, and Fukui function (FF) data, are derived within the atoms‐in‐molecules (AIM) resolution. Relaxational correction to the reactant CT FF vector is identified and qualitatively examined. The previously introduced intersecting state model (ISM) of the A ‐ B systems is generalized beyond the N ‐restricted CT energy profile and formulated in terms of the intersecting energy paraboloids of reactants, within both uncoupled (qualitative) and coupled (quantitative) formulations; here, N is the total number of electrons. The model identifies the N ‐unrestricted reaction paths in the AIM electron population space, possible when the system can exchange electrons with its environment and generally corresponding to a lower activation energy. The orientation of the reactant FF vector as a function of the hardness tensor structure is qualitatively examined in a model system consisting of two populational degrees of freedom (2 df), and the resulting conclusions are used to examine the mutual orientation of the hardness ellipses of the 2 df reactants in the A‐B systems. Predicted orientations and trends in activation barriers are discussed in the context of the hard‐soft acids and bases principle. © 1994 John Wiley & Sons, Inc.