SENSITIVITY ANALYSIS OF CHARGE-TRANSFER SYSTEMS - IN-SITU QUANTITIES,INTERSECTING STATE MODEL AND ITS IMPLICATIONS

The states of reactants in the donor (base, B)-acceptor (acid, A) syst ems are examined and the charge transfer (cr) in situ sensitivities, i ncluding the chemical potential, hardness, softness, and Fukui functio n (FF) data, are derived within the atoms-in-molecules (AIM) resolutio n. Relaxational correction to the reactant cr FF vector is identified and qualitatively examined. The previously introduced intersecting sta te model (ISM) of the A-B systems is generalized beyond the N-restrict ed cr energy profile and formulated in terms of the intersecting energ y paraboloids of reactants, within both uncoupled (qualitative) and co upled (quantitative) formulations; here, N is the total number of elec trons. The model identifies the N-unrestricted reaction paths in the A IM electron population space, possible when the system can exchange el ectrons with its environment and generally corresponding to a lower ac tivation energy. The orientation of the reactant A vector as a functio n of the hardness tenser structure is qualitatively examined in a mode l 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. Pre dicted orientations and trends in activation barriers are discussed in the context of the hard-soft acids and bases principle. (C) 1994 John Wiley and Sons, Inc.