Construction and Application of a New Dual-Hybrid Random Phase Approximation

Pál D. Mezei, G. Csonka, Adrienn Ruzsinszky, M. Kállay

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The direct random phase approximation (dRPA) combined with Kohn-Sham reference orbitals is among the most promising tools in computational chemistry and applicable in many areas of chemistry and physics. The reason for this is that it scales as N4 with the system size, which is a considerable advantage over the accurate ab initio wave function methods like standard coupled-cluster. dRPA also yields a considerably more accurate description of thermodynamic and electronic properties than standard density-functional theory methods. It is also able to describe strong static electron correlation effects even in large systems with a small or vanishing band gap missed by common single-reference methods. However, dRPA has several flaws due to its self-correlation error. In order to obtain accurate and precise reaction energies, barriers and noncovalent intra- and intermolecular interactions, we construct a new dual-hybrid dRPA (hybridization of exact and semilocal exchange in both the energy and the orbitals) and test the performance of this new functional on isogyric, isodesmic, hypohomodesmotic, homodesmotic, and hyperhomodesmotic reaction classes. We also use a test set of 14 Diels-Alder reactions, six atomization energies (AE6), 38 hydrocarbon atomization energies, and 100 reaction barrier heights (DBH24, HT-BH38, and NHT-BH38). For noncovalent complexes, we use the NCCE31 and S22 test sets. To test the intramolecular interactions, we use a set of alkane, cysteine, phenylalanine-glycine-glycine tripeptide, and monosaccharide conformers. We also discuss the delocalization and static correlation errors. We show that a universally accurate description of chemical properties can be provided by a large, 75% exact exchange mixing both in the calculation of the reference orbitals and the final energy.

Original languageEnglish
Pages (from-to)4615-4626
Number of pages12
JournalJournal of Chemical Theory and Computation
Volume11
Issue number10
DOIs
Publication statusPublished - Oct 13 2015

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Atomization
Glycine
Amino acids
Computational chemistry
Electron correlations
Alkanes
Monosaccharides
Energy barriers
Wave functions
Hydrocarbons
Phenylalanine
approximation
Electronic properties
Paraffins
Chemical properties
Density functional theory
Cysteine
atomizing
glycine
Energy gap

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Construction and Application of a New Dual-Hybrid Random Phase Approximation. / Mezei, Pál D.; Csonka, G.; Ruzsinszky, Adrienn; Kállay, M.

In: Journal of Chemical Theory and Computation, Vol. 11, No. 10, 13.10.2015, p. 4615-4626.

Research output: Contribution to journalArticle

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