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Temperature‐dependent approach to chemical reactivity concepts in density functional theory
Author(s) -
Gázquez José L.,
FrancoPérez Marco,
Ayers Paul W.,
Vela Alberto
Publication year - 2019
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.25797
Subject(s) - helmholtz free energy , density functional theory , statistical physics , reactivity (psychology) , heat capacity , thermodynamics , complement (music) , entropy (arrow of time) , theoretical physics , zero temperature , chemistry , physics , computational chemistry , quantum mechanics , complementation , medicine , biochemistry , alternative medicine , pathology , gene , phenotype
The chemical reactivity concepts of density functional theory are studied through a unified view in the temperature‐dependent approach provided by the grand canonical ensemble. This procedure leads to a more general perspective that enriches our understanding of the behavior of the average energy and its derivatives with respect to the average number of electrons, provides alternative definitions for those quantities that are “ill defined” at zero temperature, and allows one to determine the relationships among reactivity concepts at any temperature. In particular, it has been found that at high temperatures the parabolic model for reactivity indicators may be justified through the electronic entropy term in the Helmholtz free energy, and that at nonzero temperatures there is an electronic heat capacity contribution to the average energy. In summary, the unified view of the temperature‐dependent approach is an important complement to the zero‐temperature formulation that clarifies fundamental issues therein.