A new tuned range-separated density functional for the accurate calculation of second hyperpolarizabilities
dc.contributor.author
dc.date.accessioned
2020-06-11T09:56:54Z
dc.date.available
2022-10-28T05:46:33Z
dc.date.issued
2020-05-12
dc.identifier.issn
1463-9076
dc.identifier.uri
dc.description.abstract
The calculation of nonlinear optical properties (NLOPs) using density functional theory (DFT) remains a challenge in computational chemistry. Although existing range-separated functionals display the best performance for the calculation of this type of properties, their errors strongly depend on the family of molecules studied. Herein, we have explored a new strategy to empirically tune the range-separated LC-BLYP method to improve the accuracy of the calculation of the second hyperpolarizabilities (γ), which are poorly described by current density functional approximations. First, we benchmarked nine of the most accurate commonly used range-separated hybrid and optimally-tuned functionals (i.e. B3LYP, PBE0, BH&HLYP, M06-2X, MN15, ωB97XD, CAM-B3LYP, LC-BLYP and OT-LC-BLYP) for the calculation of γ using as reference the CCSD(T) values of a chemically diverse set of 60 molecules. Among these nine functionals, LC-BLYP gives the lowest average errors. We determined the value of the range-separation parameter ω required to reproduce the CCSD(T) second hyperpolarizabilities with LC-BLYP functional (ωCC) for the set of 60 molecules. Our new tuned range-separated functional, Tα-LC-BLYP, employs a quadratic correlation between ωCC and a molecular descriptor in terms of the linear polarizability and the number of electrons of the molecule. The average error of the γ values obtained with Tα-LC-BLYP is reduced by half or more as compared with the most accurate among the nine density functional approximations benchmarked
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation.isformatof
Versió Potprint del document publicat a: https://doi.org/10.1039/D0CP01291B
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© Physical Chemistry Chemical Physics, 2020, vol. undef, núm. undef, p. undef
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Articles publicats (D-Q)
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Tots els drets reservats
dc.source
Besalú Sala, Pau Sitkiewicz, Sebastian P. Salvador Sedano, Pedro Matito i Gras, Eduard Luis Luis, Josep Maria 2020 A new tuned range-separated density functional for the accurate calculation of second hyperpolarizabilities Physical Chemistry Chemical Physics undef undef undef
dc.title
A new tuned range-separated density functional for the accurate calculation of second hyperpolarizabilities
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2021-05-12T00:00:00Z
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2021-05-12
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
031590
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1463-9084