Pii: S0166-1280(99)00245-6
نویسندگان
چکیده
The non-specific solvent effects in neutral dipolar (or better yet, effective dipolar) solvents were discussed in the literature with success. However the situation is not so clear when the solvent is an electrolyte, where the reaction field approach is no longer valid. In the present communication we present a theory based on the Mean Spherical Scaling Approximation in which the system is encapsulated in a ionic cloud that is represented by an equivalent capacitor of shape determined by precise prescriptions derived from exact relations and sum rules. The construction of the equivalent capacitor depends on the geometry of the system, on the nature of the solvent and on the nature and concentration of the ions. The treatment proposed here satisfies exact relations like the Stillinger–Lovett sum rules, the perfect screening sum rules, and the high and low coupling conditions and constitutes an interpolation scheme between exact high density and low density limits in it simplest form. The calculation is illustrated with an example of an ellipsoidal cavity. q 1999 Elsevier Science B.V. All rights reserved.
منابع مشابه
Pii: S0166-1280(99)00011-1
s / Journal of Molecular Structure (Theochem) 463 (1999) 41–43 43 Potential energy surfaces and dynamics of chemical reactions
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Local exchange-correlation functionals are defined for different systems with spherical symmetry, by requiring that they reproduce the correct exchange-correlation energy and exchange-correlation potential (up to a constant). For comparison, the results with the uniform electron gas local density approximation and a generalized gradient approximation are also shown. q 2000 Elsevier Science B.V....
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Systematic computational studies of the XNO (X H, F, Cl, and OH) molecular systems with complete basis set and gaussian ab initio methods were used for accurate evaluations of their enthalpies of formation, bond dissociation energies, relative energies, and activation barriers of rotation and isomerization. It was demonstrated that experimentally determined enthalpies of formation for nitroge...
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The Direct Reaction Field approach is briefly reviewed. Preliminary reports of the calculations on solvent induced shifts in the p* ← n transition of acetone in various solvents, and the dissociation of tert-butyl chloride in water are given. q 1999 Elsevier Science B.V. All rights reserved.
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We consider the minimal unsatissablity problem MU(k) for proposi-tional formulas in conjunctive normal form (CNF) over n variables and n + k clauses, where k is xed. It will be shown that MU(k) is in NP. Based on the non{deterministic algorithm we prove for MU(2) that after a simpliication by resolving over variables occuring at most once positively or at most once negatively such minimal unsat...
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