Pitfall in simulations of vibronic TD-DFT spectra: diagnosis and assessment
dc.contributor.author
dc.date.accessioned
2024-02-05T08:20:37Z
dc.date.available
2024-02-05T08:20:37Z
dc.date.issued
2023-10-16
dc.identifier.issn
1463-9076
dc.identifier.uri
dc.description.abstract
In this Communication, we study the effect of spurious oscillations in the profiles of energy derivatives with respect to nuclear coordinates calculated with density functional approximations (DFAs) for formaldehyde, pyridine, and furan in their ground and electronic excited states. These spurious oscillations, which can only be removed using extensive integration grids that increase enormously the CPU cost of DFA calculations, are significant in the case of third- and fourth-order energy derivatives of the ground and excited states computed by M06-2X and ωB97X functionals. The errors in question propagate to anharmonic vibronic spectra computed under the Franck-Condon approximation, i.e., positions and intensities of vibronic transitions are affected to a large extent (shifts as significant as hundreds of cm−1 were observed). On the other hand, the LC-BLYP and CAM-B3LYP functionals show a much less pronounced effect due to spurious oscillations. Based on the results presented herein, we recommend either LC-BLYP or CAM-B3LYP with integration grids (250, 974) (or larger) for numerically stable simulations of vibronic spectra including anharmonic effects
dc.format.extent
5 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation.isformatof
Reproducció digital del document publicat a: https://doi.org/10.1039/D3CP04276F
dc.relation.ispartof
Physical Chemistry Chemical Physics, 2023, vol. 25, núm. 44, p. 30193-30197
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Articles publicats (D-Q)
dc.rights
Reconeixement-NoComercial 4.0 Internacional
dc.rights.uri
dc.source
Sitkiewicz, Sebastian P. Matito i Gras, Eduard Luis Luis, Josep Maria Zaleśny, Robert 2023 Pitfall in simulations of vibronic TD-DFT spectra: diagnosis and assessment Physical Chemistry Chemical Physics 25 44 30193 30197
dc.subject
dc.title
Pitfall in simulations of vibronic TD-DFT spectra: diagnosis and assessment
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
037697
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1463-9084