How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?

We show that properties of molecules with low-frequency modes calculated with density functional approximations (DFAs) suffer from spurious oscillations along the nuclear displacement coordinate due to numerical integration errors. Occasionally, the problem can be alleviated using extensive integrat...

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Autores: Sitkiewicz, Sebastian P., Zaleśny, Robert, Ramos Cordoba, Eloy, Luis Luis, Josep Maria, Matito i Gras, Eduard
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
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:10256/21702
Acceso en línea:http://hdl.handle.net/10256/21702
Access Level:acceso abierto
Palabra clave:Teoria del funcional de densitat
Density functionals
Molècules
Molecules
Espectres vibracionals
Vibrational spectra
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spelling How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?Sitkiewicz, Sebastian P.Zaleśny, RobertRamos Cordoba, EloyLuis Luis, Josep MariaMatito i Gras, EduardTeoria del funcional de densitatDensity functionalsMolèculesMoleculesEspectres vibracionalsVibrational spectraWe show that properties of molecules with low-frequency modes calculated with density functional approximations (DFAs) suffer from spurious oscillations along the nuclear displacement coordinate due to numerical integration errors. Occasionally, the problem can be alleviated using extensive integration grids that compromise the favorable cost-accuracy ratio of DFAs. Since spurious oscillations are difficult to predict or identify, DFAs are exposed to severe performance errors in IR and Raman intensities and frequencies or vibrational contributions to any molecular property. Using Fourier spectral analysis and digital signal processing techniques, we identify and quantify the error due to these oscillations for 45 widely used DFAs. LC-BLYP and BH&H are revealed as the only functionals showing robustness against the spurious oscillations of various energy, dipole moment, and polarizability derivatives with respect to a nuclear displacement coordinate. Given the ubiquitous nature of molecules with low-frequency modes, we warrant caution in using modern DFAs to simulate vibrational spectroscopiesGrants PGC2018-098212-B-C21, PGC2018- 098212-B-C22, and IJCI-2017-34658 funded by MCIN/AEI/ 10.13039/501100011033 and “FEDER Una manera de hacer Europa”, and the grants funded by Diputación Foral de Gipuzkoa (Grant 2019-CIEN-000092-01), and Gobierno Vasco (Grants IT1254-19, PRE_2020_2_0015, and PIBA19- 0004) are acknowledged. R.Z. gratefully acknowledges support from the Polish National Science Center (Grant 2018/30/E/ ST4/00457)Open Access funding provided thanks to the CRUE-CSIC agreement with ACSAmerican Chemical Society (ACS)Agencia Estatal de Investigación2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/21702Journal of Physical Chemistry Letters, 2022, vol. 13, núm. 25, p. 5963 -5968Articles 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.jpclett.2c01278info:eu-repo/semantics/altIdentifier/eissn/1948-7185PGC2018-098212-B-C22info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/217022026-05-29T05:05:01Z
dc.title.none.fl_str_mv How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
title How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
spellingShingle How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
Sitkiewicz, Sebastian P.
Teoria del funcional de densitat
Density functionals
Molècules
Molecules
Espectres vibracionals
Vibrational spectra
title_short How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
title_full How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
title_fullStr How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
title_full_unstemmed How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
title_sort How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?
dc.creator.none.fl_str_mv Sitkiewicz, Sebastian P.
Zaleśny, Robert
Ramos Cordoba, Eloy
Luis Luis, Josep Maria
Matito i Gras, Eduard
author Sitkiewicz, Sebastian P.
author_facet Sitkiewicz, Sebastian P.
Zaleśny, Robert
Ramos Cordoba, Eloy
Luis Luis, Josep Maria
Matito i Gras, Eduard
author_role author
author2 Zaleśny, Robert
Ramos Cordoba, Eloy
Luis Luis, Josep Maria
Matito i Gras, Eduard
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Teoria del funcional de densitat
Density functionals
Molècules
Molecules
Espectres vibracionals
Vibrational spectra
topic Teoria del funcional de densitat
Density functionals
Molècules
Molecules
Espectres vibracionals
Vibrational spectra
description We show that properties of molecules with low-frequency modes calculated with density functional approximations (DFAs) suffer from spurious oscillations along the nuclear displacement coordinate due to numerical integration errors. Occasionally, the problem can be alleviated using extensive integration grids that compromise the favorable cost-accuracy ratio of DFAs. Since spurious oscillations are difficult to predict or identify, DFAs are exposed to severe performance errors in IR and Raman intensities and frequencies or vibrational contributions to any molecular property. Using Fourier spectral analysis and digital signal processing techniques, we identify and quantify the error due to these oscillations for 45 widely used DFAs. LC-BLYP and BH&H are revealed as the only functionals showing robustness against the spurious oscillations of various energy, dipole moment, and polarizability derivatives with respect to a nuclear displacement coordinate. Given the ubiquitous nature of molecules with low-frequency modes, we warrant caution in using modern DFAs to simulate vibrational spectroscopies
publishDate 2022
dc.date.none.fl_str_mv 2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/21702
url http://hdl.handle.net/10256/21702
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.jpclett.2c01278
info:eu-repo/semantics/altIdentifier/eissn/1948-7185
PGC2018-098212-B-C22
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Journal of Physical Chemistry Letters, 2022, vol. 13, núm. 25, p. 5963 -5968
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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score 15,812429

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