Spurious Oscillations Caused by Density Functional Approximations: Who is to Blame? Exchange or Correlation?
dc.contributor.author
dc.date.accessioned
2024-06-19T07:32:24Z
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2024-06-19T07:32:24Z
dc.date.issued
2024-04-03
dc.identifier.issn
1549-9618
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dc.description.abstract
We analyze the varying susceptibilities of different density functional approximations (DFAs) to present spurious oscillations on the profiles of several vibrational properties. Among other problems, these spurious oscillations cause significant errors in harmonic and anharmonic IR and Raman frequencies and intensities. This work hinges on a judicious strategy to dissect the exchange and correlation components of DFAs and pinpoint the origins of these oscillations. We identify spurious oscillations in derivatives of all energy components with respect to nuclear displacements, including those energy terms that do not involve numerical integrations. These indirect spurious oscillations are attributed to suboptimal electron densities resulting from a self-consistent field procedure using a DFA that exhibits direct spurious oscillations. Direct oscillations stem from inaccurate numerical integration of the exchange and correlation energy density functionals. A thorough analysis of direct spurious oscillations reveals that only a handful of exchange and correlation components are insensitive to spurious oscillations, giving rise to three families of functionals, BH&H, LSDA, and BLYP. Among the functionals in these families, we encounter four widespread DFAs: BLYP, B3LYP, LC-BLYP, and CAM-B3LYP. Certain DFAs like PBE appear less sensitive to spurious oscillations due to compensatory cancellations between their energy components. Additionally, we found non-negligible but small oscillations in PBE and TPSS, which could be safely employed provided a sufficiently large integration grid is used in the calculations. These findings hint at the key components of current approximations to be improved and emphasize the necessity to develop accurate DFAs suitable for studying molecular spectroscopies
dc.description.sponsorship
E.M.,J.M.L., and E.R.-C. acknowledge funding from AgenciaEspañ ola de Investigación, “FEDER Una manera de hacerEuropa” (PID2022-140666NB-C21 and PID2022-140666NB-C22), the Donostia International Physics Center (DIPC-INV-003132, DIPC-INV-003133, and R.F.R. postdoctoral fellow-ship), the Generalitat de Catalunya (2021SGR00623), and thegrants funded by the Gobierno Vasco (IT1584-22, andPIBA_2023_1_0055
Open Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
PID2022-140666NB-C22
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Reproducció digital del document publicat a: https://doi.org/10.1021/acs.jctc.3c01339
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Journal of Chemical Theory and Computation, 2024, vol. 20, núm. 8, p. 3144–3153
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Articles publicats (D-Q)
dc.rights
Attribution 4.0 International
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dc.subject
dc.title
Spurious Oscillations Caused by Density Functional Approximations: Who is to Blame? Exchange or Correlation?
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-140666NB-C22/ES/ESTRUCTURA ELECTRONICA, PROPIEDADES Y REACTIVIDAD DE MOLECULAS BAJO CAMPOS ELECTRICOS/
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
038918
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
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dc.relation.ProjectAcronym
dc.identifier.eissn
1549-9626