The quest for a universal density functional: The accuracy of density functionals across a broad spectrum of databases in chemistry and physics

摘要

Kohn-Sham density functional theory is in principle an exact formulation ofquantum mechanical electronic structure theory, but in practice we have to relyon approximate exchange-correlation (xc) functionals. The objective of our workhas been to design an xc functional with broad accuracy across as wide anexpanse of chemistry and physics as possible, leading-as a long-range goal-to afunctional with good accuracy for all problems, i.e., a universal functional.To guide our path toward that goal and to measure our progress, we havedeveloped-building on earlier work in our group-a set of databases of referencedata for a variety of energetic and structural properties in chemistry andphysics. These databases include energies of molecular processes such asatomization, complexation, proton addition, and ionization; they also includemolecular geometries and solid-state lattice constants, chemical reactionbarrier heights, and cohesive energies and band gaps of solids. For the presentpaper we gather many of these databases into four comprehensive databases, twowith 384 energetic data for chemistry and solid-state physics and another twowith 68 structural data for chemistry and solid-state physics, and we test 2wave function methods and 77 density functionals (12 Minnesota meta functionalsand 65 others) in a consistent way across this same broad set of data. Weespecially highlight the Minnesota density functionals, but the results havebroader implications in that one may see the successes and failures of manykinds of density functionals when they are all applied to the same data.Therefore the results provide a status report on the quest for a universalfunctional.