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

• Published in: Philosophical transactions of the Royal Society of London. Series A: Mathematical, physical, and engineering sciences Vol. 372; no. 2011; p. 20120476
• Main Authors: Peverati, Roberto, Truhlar, Donald G.
• Format: Journal Article
• Language: English
• Published: England The Royal Society Publishing 13.03.2014
• Subjects: Chemical Reaction Barrier Heights; Energy Of Reaction; Exchange-Correlation Functionals; exchangecorrelation functionals; Lattice Constants; Non-Covalent Interaction Energies; Thermochemistry Of Molecules And Solids; exchange–correlation functionals; chemical reaction barrier heights; energy of reaction; non-covalent interaction energies; lattice constants; thermochemistry of molecules and solids
• ISSN: 1364-503X; 1471-2962
• DOI: 10.1098/rsta.2012.0476

KohnSham density functional theory is in principle an exact formulation of quantum mechanical electronic structure theory, but in practice we have to rely on approximate exchangecorrelation (xc) functionals. The objective of our work has been to design an xc functional with broad accuracy across as wide an expanse of chemistry and physics as possible, leadingas a long-range goalto a functional with good accuracy for all problems, i.e. a universal functional. To guide our path towards that goal and to measure our progress, we have developedbuilding on earlier work of our groupa set of databases of reference data for a variety of energetic and structural properties in chemistry and physics. These databases include energies of molecular processes, such as atomization, complexation, proton addition and ionization; they also include molecular geometries and solid-state lattice constants, chemical reaction barrier heights, and cohesive energies and band gaps of solids. For this paper, we gather many of these databases into four comprehensive databases, two with 384 energetic data for chemistry and solid-state physics and another two with 68 structural data for chemistry and solid-state physics, and we test two wave function methods and 77 density functionals (12 Minnesota meta functionals and 65 others) in a consistent way across this same broad set of data. We especially highlight the Minnesota density functionals, but the results have broader implications in that one may see the successes and failures of many kinds of density functionals when they are all applied to the same data. Therefore, the results provide a status report on the quest for a universal functional.