Use of the rVV10 nonlocal correlation functional in the B97M-V density functional: defining B97M-rV and related functionals
Use of the rVV10 nonlocal correlation functional in the B97M-V density functional: defining B97M-rV and related functionals
The VV10 and rVV10 nonlocal correlation functionals are consistently implemented and assessed, with the goal of determining if the rVV10 nonlocal correlation functional can replace the VV10 nonlocal correlation functional in the recently developed B97M-V density functional, to give the B97M-rV density functional. Along the way, four density functionals are simultaneously tested: VV10, rVV10, B97M-V, and B97M-rV. An initial assessment is carried out across the S22 data set, and the short-range damping variable, b, is varied for all four density functionals in order to determine the sensitivity of the functionals to the empirical parameter. The results of this test indicate that a value of b = 6 (fortuitously the same as that in B97M-V) is suitable for B97M-rV. The functionals are then compared across an extensive database of interaction energies, and it is demonstrated that B97M-rV either matches or outperforms B97M-V for all of the tests considered. Finally, the optimization of b across the S22 data set is extended to two range-separated hybrid density functionals, wB97X-V and wB97M-V, and a value of b = 6.2 is recommended for both wB97X-rV and wB97M-rV.
35-40
Mardirossian, Narbe
6dc65ee1-19a9-490e-83e6-6984a64bb7f9
Ruiz Pestana, Luis
f610dfad-5a5a-4c37-b8e9-5911ce614364
Womack, James C.
ef9e1954-4a38-4e89-bf25-741a0738e85b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a
December 2016
Mardirossian, Narbe
6dc65ee1-19a9-490e-83e6-6984a64bb7f9
Ruiz Pestana, Luis
f610dfad-5a5a-4c37-b8e9-5911ce614364
Womack, James C.
ef9e1954-4a38-4e89-bf25-741a0738e85b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a
Mardirossian, Narbe, Ruiz Pestana, Luis, Womack, James C., Skylaris, Chris-Kriton, Head-Gordon, Teresa and Head-Gordon, Martin
(2016)
Use of the rVV10 nonlocal correlation functional in the B97M-V density functional: defining B97M-rV and related functionals.
The Journal of Physical Chemistry Letters, 2017 (8), .
(doi:10.1021/acs.jpclett.6b02527).
Abstract
The VV10 and rVV10 nonlocal correlation functionals are consistently implemented and assessed, with the goal of determining if the rVV10 nonlocal correlation functional can replace the VV10 nonlocal correlation functional in the recently developed B97M-V density functional, to give the B97M-rV density functional. Along the way, four density functionals are simultaneously tested: VV10, rVV10, B97M-V, and B97M-rV. An initial assessment is carried out across the S22 data set, and the short-range damping variable, b, is varied for all four density functionals in order to determine the sensitivity of the functionals to the empirical parameter. The results of this test indicate that a value of b = 6 (fortuitously the same as that in B97M-V) is suitable for B97M-rV. The functionals are then compared across an extensive database of interaction energies, and it is demonstrated that B97M-rV either matches or outperforms B97M-V for all of the tests considered. Finally, the optimization of b across the S22 data set is extended to two range-separated hybrid density functionals, wB97X-V and wB97M-V, and a value of b = 6.2 is recommended for both wB97X-rV and wB97M-rV.
Text
paper_accepted_manuscript.pdf
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More information
Accepted/In Press date: 6 December 2016
e-pub ahead of print date: 12 December 2016
Published date: December 2016
Additional Information:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.6b02527.
For further details, see the ACS Journal Publishing Agreement User's Guide (section II, part 7):
http://pubs.acs.org/userimages/ContentEditor/1285231362937/jpa_user_guide.pdf
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Computational Systems Chemistry
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Local EPrints ID: 403871
URI: http://eprints.soton.ac.uk/id/eprint/403871
ISSN: 1948-7185
PURE UUID: 0855334c-87b3-4c17-bc12-c504e0876603
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Date deposited: 14 Dec 2016 13:33
Last modified: 16 Mar 2024 03:51
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Author:
Narbe Mardirossian
Author:
Luis Ruiz Pestana
Author:
James C. Womack
Author:
Teresa Head-Gordon
Author:
Martin Head-Gordon
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