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Wavefunction-like Correlation Model for Use in Hybrid Density Functionals

Cite this: J. Chem. Theory Comput. 2018, 14, 9, 4590–4599
Publication Date (Web):August 6, 2018
https://doi.org/10.1021/acs.jctc.8b00337
Copyright © 2018 American Chemical Society

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    Abstract

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    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.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jctc.8b00337.

    • Tables of coefficients csγ used in eq 38 and tables of individual atomization energies and barrier heights for the test sets mentioned in the text (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Golokesh Santra, Minsik Cho, Jan M. L. Martin. Exploring Avenues beyond Revised DSD Functionals: I. Range Separation, with xDSD as a Special Case. The Journal of Physical Chemistry A 2021, 125 (21) , 4614-4627. https://doi.org/10.1021/acs.jpca.1c01294
    2. Zack M. Williams, Timothy C. Wiles, Frederick R. Manby. Accurate Hybrid Density Functionals with UW12 Correlation. Journal of Chemical Theory and Computation 2020, 16 (10) , 6176-6194. https://doi.org/10.1021/acs.jctc.0c00442
    3. Johannes T. Margraf, Christian Kunkel, Karsten Reuter. Towards density functional approximations from coupled cluster correlation energy densities. The Journal of Chemical Physics 2019, 150 (24) https://doi.org/10.1063/1.5094788

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