Constraints upon Functionals of the 1-Matrix, Universal Properties of Natural Orbitals, and the Fallacy of the Collins "Conjecture"

Reliability of quantum-chemical calculations based upon the density functional theory and its 1-matrix counterpart hinges upon minimizing the extent of empirical parameterization in the approximate energy expressions of these formalisms while imposing as many rigorous constraints upon them as possible. The recently uncovered universal properties of the natural orbitals facilitate the construction of such constraints for the 1-matrix functionals. The benefits of their employment in the validation of these functionals are vividly demonstrated by a critical review of the three incarnations of the so-called Collins conjecture. Although the incorporation of rigorous definitions of the correlation energy and entropy, and the identification of individual potential energy hypersurfaces as probable domains of its applicability turn the originally published unsubstantiated claim into a proper conjecture, the resulting formalism is found to be merely a conduit for incorporation of static correlation effects in electronic structure calculations that is unlikely to allow attaining chemical accuracy.