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

Roberto Peverati, Donald G. Truhlar

Research output: Contribution to journalReview article

412 Scopus citations

Abstract

Kohn-Sham density functional theory is in principle an exact formulation of quantum mechanical electronic structure theory, but in practice we have to rely on approximate exchange-correlation (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, leading-as a long-range goal-to 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 developed-building on earlier work of our group-a 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.

Original languageEnglish (US)
Article number20120476
JournalPhilosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
Volume372
Issue number2011
DOIs
StatePublished - Mar 13 2014

Keywords

  • Chemical reaction barrier heights
  • Energy of reaction
  • Exchange-correlation functionals
  • Lattice constants
  • Non-covalent interaction energies
  • Thermochemistry of molecules and solids

Fingerprint Dive into the research topics of 'Quest for a universal density functional: The accuracy of density functionals across a broad spectrum of databases in chemistry and physics'. Together they form a unique fingerprint.

  • Cite this