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Local kinetic energy and local temperature in the density‐functional theory of electronic structure
Author(s) -
Ayers Paul W.,
Parr Robert G.,
Nagy Agnes
Publication year - 2002
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.989
Subject(s) - kinetic energy , gaussian , orbital free density functional theory , density functional theory , statistical physics , pair distribution function , entropy (arrow of time) , electronic structure , distribution function , chemistry , quantum , electron , physics , local density approximation , thermodynamics , quantum mechanics
Various thermodynamic elements of the density functional theory of electronic structure are reviewed and clarified. Detailed argumentation is given for the particular “del dot del” definition of the local kinetic energy density and local temperature. The temperature measures the “nighness” of an electron pair, thus playing a key role in quantitative (exchange and kinetic energy functionals) and qualitative (electron localization functions) tools based on the electron pair density. Two different derivations are given of the Gaussian model for the phase‐space distribution function, from which one obtains an approximation to the entropy of the charge distribution. The full thermodynamic description is briefly discussed. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002