Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes

This work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability...

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Autores: Zaleśny, Robert, Medved, Miroslav, Sitkiewicz, Sebastian P., Matito i Gras, Eduard, Luis Luis, Josep Maria
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/28569
Acceso en línea:http://hdl.handle.net/10256/28569
https://hdl.handle.net/10256/28569
Access Level:acceso abierto
Palabra clave:Funcional de densitat, Teoria del
Density functionals
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spelling Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded ComplexesZaleśny, RobertMedved, MiroslavSitkiewicz, Sebastian P.Matito i Gras, EduardLuis Luis, Josep MariaFuncional de densitat, Teoria delDensity functionalsThis work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability and the first and second hyperpolarizabilities, using the CCSD(T)/aug-cc-pVTZ level of theory as reference. For all the studied properties, the average absolute errors below 20% can only be obtained using the CAM-B3LYP functional, while LC-BLYP and MN15 are shown to be only slightly less accurate (average absolute errors not exceeding 30%). Among Minnesota density functionals, i.e., M06, M06-2X, and MN15, we only recommend the latter one, which quite accurately predicts the electronic and vibrational (hyper)polarizabilities. We also analyze the optimal tuning of the range-separation parameter μ for the LC-BLYP functional, finding that this approach does not bring any systematic improvement in the predictions of electronic and vibrational (hyper)polarizabilities and the accuracy of computed properties is largely system-dependent. Finally, we report huge errors in predicting the vibrational second hyperpolarizability by ωB97X, M06, and M06-2X functionals. Based on the explicit evaluation of anharmonic terms contributing to the second hyperpolarizability, this failure is traced down to a poor determination of third- and fourth-order energy derivatives with respect to normal modes. These results reveal serious flaws of some density functional approximations and suggest caution in selecting the appropriate functional to calculate not only electronic and vibrational (hyper)polarizabilities but also other molecular properties that contain vibrational anharmonic contributionsR.Z. acknowledges financial support by the Polish National Science Centre (Grant No. 2015/19/B/ST4/01881). M.M. acknowledges the Slovak Research and Development Agency (project no. APVV-15-0105) and CMST COST Action CM1405 MOLIM: MOLecules In Motion. J.M.L. and E.M. are grateful for financial support from the Spanish MINECO CTQ2014-52525-P (E.M. and J.M.L.) and EUIN2017-88605 (E.M.), and to the Catalan DIUE 2014SGR931 (J.M.L.). S.P.S. acknowledges the Basque Government for funding through a predoctoral fellowship (PRE 2018 2 0200)American Chemical Society2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/28569https://hdl.handle.net/10256/28569© Journal of Chemical Theory and Computation, 2019, vol. 15, núm. 6, p. 3570-3579Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.9b00139info:eu-repo/semantics/altIdentifier/issn/1549-9618info:eu-repo/semantics/altIdentifier/eissn/1549-9626InChttps://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/285692026-05-29T05:05:01Z
dc.title.none.fl_str_mv Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
title Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
spellingShingle Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
Zaleśny, Robert
Funcional de densitat, Teoria del
Density functionals
title_short Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
title_full Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
title_fullStr Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
title_full_unstemmed Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
title_sort Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes
dc.creator.none.fl_str_mv Zaleśny, Robert
Medved, Miroslav
Sitkiewicz, Sebastian P.
Matito i Gras, Eduard
Luis Luis, Josep Maria
author Zaleśny, Robert
author_facet Zaleśny, Robert
Medved, Miroslav
Sitkiewicz, Sebastian P.
Matito i Gras, Eduard
Luis Luis, Josep Maria
author_role author
author2 Medved, Miroslav
Sitkiewicz, Sebastian P.
Matito i Gras, Eduard
Luis Luis, Josep Maria
author2_role author
author
author
author
dc.subject.none.fl_str_mv Funcional de densitat, Teoria del
Density functionals
topic Funcional de densitat, Teoria del
Density functionals
description This work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability and the first and second hyperpolarizabilities, using the CCSD(T)/aug-cc-pVTZ level of theory as reference. For all the studied properties, the average absolute errors below 20% can only be obtained using the CAM-B3LYP functional, while LC-BLYP and MN15 are shown to be only slightly less accurate (average absolute errors not exceeding 30%). Among Minnesota density functionals, i.e., M06, M06-2X, and MN15, we only recommend the latter one, which quite accurately predicts the electronic and vibrational (hyper)polarizabilities. We also analyze the optimal tuning of the range-separation parameter μ for the LC-BLYP functional, finding that this approach does not bring any systematic improvement in the predictions of electronic and vibrational (hyper)polarizabilities and the accuracy of computed properties is largely system-dependent. Finally, we report huge errors in predicting the vibrational second hyperpolarizability by ωB97X, M06, and M06-2X functionals. Based on the explicit evaluation of anharmonic terms contributing to the second hyperpolarizability, this failure is traced down to a poor determination of third- and fourth-order energy derivatives with respect to normal modes. These results reveal serious flaws of some density functional approximations and suggest caution in selecting the appropriate functional to calculate not only electronic and vibrational (hyper)polarizabilities but also other molecular properties that contain vibrational anharmonic contributions
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/28569
https://hdl.handle.net/10256/28569
url http://hdl.handle.net/10256/28569
https://hdl.handle.net/10256/28569
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.9b00139
info:eu-repo/semantics/altIdentifier/issn/1549-9618
info:eu-repo/semantics/altIdentifier/eissn/1549-9626
dc.rights.none.fl_str_mv InC
https://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv InC
https://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv © Journal of Chemical Theory and Computation, 2019, vol. 15, núm. 6, p. 3570-3579
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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