The Pursuit of Fallacy in Density Functional Theory: The Quest for Exchange and Correlation, the Rigorous Treatment of Exchange in the Kohn-Sham Formalism and the Continuing Search for Correlation

As pointed out in the paper preceding this one, in the case of functionals whose independent variable must obey conditions of integral normalization, conventional functional differentiation, defined in terms of an arbitrary test function, is generally inapplicable and functional derivatives with respect to the density must be evaluated through the alternative and widely used limiting procedure based on the Dirac delta function. This leads to the determination of the rate of change of the dependent variable with respect to its independent variable at each isolated pair, , that may not be part of a functional (a set of ordered pairs). This extends the concept of functional derivative to expectation values of operators with respect to wave functions leading to a density even if the wave functions (and expectation values) do not form functionals. This new formulation of functional differentiation forms the basis for the study of the mathematical integrity of a number of concepts in density functional theory (DFT) such as the existence of a universal functional of the density, of orbital-free density functional theory, the derivative discontinuity of the exchange and correlation functional and the extension of DFT to open systems characterized by densities with fractional normalization. It is shown that no universal functional exists but, rather, a universal process based only on the density and independent of the possible existence of a potential, leads to unique functionals of the density determined through the minimization procedure of the constrained search. The mathematical integrity of two methodologies proposed for the treatment of the Coulomb interaction, the self-interaction free method and the optimized effective potential method is examined and the methodologies are compared in terms of numerical calculations. As emerges from this analysis, the optimized effective potential method is found to be numerically approximate but formally invalid, contrary to the rigorously exact results of the self-interaction-free method.

Functionals and Functional Derivatives of Wave Functions and Densities

It is shown that the process of conventional functional differentiation does not apply to functionals whose domain (and possibly range) is subject to the condition of integral normalization, as is the case with respect to a domain defined by wave functions or densities, in which there exists no neighborhood about a given element in the domain defined by arbitrary variations that also lie in the domain. This is remedied through the generalization of the domain of a functional to include distributions in the form of , where ?is the Dirac delta function and is a real number. This allows the determination of the rate of change of a functional with respect to changes of the independent variable determined at each point of the domain, with no reference needed to the values of the functional at different functions in its domain. One feature of the formalism is the determination of rates of change of general expectation values (that may not necessarily be functionals of the density) with respect to the wave functions or the densities determined by the wave functions forming the expectation value. It is also shown that ignoring the conditions of conventional functional differentiation can lead to false proofs, illustrated through a flaw in the proof that all densities defined on a lattice are -representable. In a companion paper, the mathematical integrity of a number of long-standing concepts in density functional theory are studied in terms of the formalism developed here.