物理化学学报 >> 2018, Vol. 34 >> Issue (6): 699-707.doi: 10.3866/PKU.WHXB201711221

所属专题： 密度泛函理论中的化学概念特刊

GEERLINGS Paul*(),DE PROFT Frank,FIAS Stijn

Paul GEERLINGS*(),Frank DE PROFT,Stijn FIAS

**摘要： **

In view of its use as reactivity theory, Conceptual Density Functional Theory (DFT), introduced by Parr *et al*., has mainly concentrated up to now on the *E* = *E*[*N*, *v*] functional. However, different ensemble representations can be used involving other variables also, such as *ρ* and *μ*. In this study, these different ensemble representations (*E*, *?*, *F*, and R) are briefly reviewed. Particular attention is then given to the corresponding second-order (functional) derivatives, and their analogies with the second-order derivatives of thermodynamic state functions *U*, *F*, *H*, and *G*, which are related to each other *via* Legendre transformations, just as the DFT functionals (Nalewajski and Parr, 1982). Starting from an analysis of the convexity/concavity of the DFT functionals, for which explicit proofs are discussed for some cases, the positive/negative definiteness of the associated kernels is derived and a detailed comparison is made with the thermodynamic derivatives.The stability conditions in thermodynamics are similar in structure to the convexity/concavity conditions for the DFT functionals. Thus, the DFT functionals are scrutinized based on the convexity/concavity of their two variables, to yield the possibility of establishing a relationship between the three second-order reactivity descriptors derived from the considered functional. Considering two ensemble representations, *F* and *?*, *F* is eliminated as it has two dependent (extensive) variables, *N* and *ρ*. For *?*, on the other hand, which is concave for both of its intensive variables (*μ* and *υ*), an inequality is derived from its three second-order (functional) derivatives: the global softness, the local softness, and the softness kernel. Combined with the negative value of the diagonal element of the linear response function, this inequality is shown to be compatible with the Berkowitz-Parr relationship, which relates the functional derivatives of *ρ* with *υ*, at constant *N* and *μ*. This was recently at stake upon quantifying Kohn’s Nearsightedness of Electronic Matter. The analogy of the resulting inequality and the thermodynamic inequality for the *G* derivatives is highlighted. Potential research paths for this study are briefly addressed; the analogies between finite-temperature DFT response functions and their thermodynamic counterparts and the quest for analogous relationships, as derived in this paper, for DFT functionals that are analogues of entropy-dimensioned thermodynamic functions such as the Massieu function.