Wavefunction-like correlation model for use in hybrid density functionals

Timothy C. Wiles, Frederick R. Manby*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

1 Citation (Scopus)
94 Downloads (Pure)

Abstract

We present Unsöld-W12 (UW12), an approximation to the correlation energy of molecules that is an explicit functional of the single-particle reduced-density matrix. The approximation resembles one part of modern explicitly correlated second-order Møller-Plesset (MP2) theory and is intended as an alternative to MP2 in double-hybrid exchange-correlation functionals. Orbital optimization with UW12 is straightforward, and the UW12 energy is evaluated without a double summation over unoccupied orbitals, leading to a faster basis-set convergence than is seen in double-hybrid functionals. We suggest a one-parameter hybrid exchange-correlation functional XCH-BLYP-UW12. XCH-BLYP-UW12 is similar to double-hybrid functionals, but contains UW12 correlation instead of MP2 correlation. We find that XCH-BLYP-UW12 is more accurate than the existing double-hybrid functional B2-PLYP for small-molecule main-group reaction barrier heights and has roughly the same accuracy as the existing hybrid functional B3LYP for atomization energies.

Original languageEnglish
Pages (from-to)4590-4599
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume14
Issue number9
Early online date6 Aug 2018
DOIs
Publication statusPublished - 11 Sep 2018

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