Skip to content

Wavefunction-like correlation model for use in hybrid density functionals

Research output: Contribution to journalArticle

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
DateAccepted/In press - 6 Aug 2018
DateE-pub ahead of print - 6 Aug 2018
DatePublished (current) - 11 Sep 2018

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.

Download statistics

No data available

Documents

Documents

  • Full-text PDF (accepted author manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via ACS at https://pubs.acs.org/doi/10.1021/acs.jctc.8b00337 . Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 384 KB, PDF document

DOI

View research connections

Related faculties, schools or groups