On the chemical potential/electronegativity equalization in density functional theory

• Autorzy: Nalewajski R.F.
• Języki publikacji: EN

Abstrakty

EN

General variational principles of the Kohn-Sham (KS) density functional theory are interpreted as the corresponding chemical potential/electronegativity equalization equations. The unconstrained (ground-state) and constrained (excited) electron configuratons are examined for both the system global description and for the case of its partitioning into mutually closed subsystems, e.g., reactants. The chemical potential discontinuity for the integer numbers of electrons at zero temperature is stressed, and the KS orbital description of he charge transfer (CT) between reactants is discussed. Using the appropriate ensemble formulation of the KS theory thein situ chemical potential/electronegativity difference, the driving 'force' behind the inter-reactant CT, is linked to the relevant KS frontier eigenvalues of polarized reactants.

Słowa kluczowe

EN

variational principles; equilibria in molecular systems; reactive systems; density functional theory; Kohn-Sham theory; chemical potential equalization; electronegativity; charge transfer processes

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 1998
• Tom: Vol. 72, nr 7S
• Strony: 1763--1778
• Opis fizyczny: Bibliogr. 31 poz.

Twórcy

autor

Nalewajski R.F.

• K. Gumiński Department of Theoretical Chemistry Jagiellonian University R. Ingardena 3 30-060 Cracow Poland