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dc.contributor.authorCornaton, Yann
dc.contributor.authorRingholm, Magnus
dc.contributor.authorLouant, Orian
dc.contributor.authorRuud, Kenneth
dc.date.accessioned2017-03-09T12:27:04Z
dc.date.available2017-03-09T12:27:04Z
dc.date.issued2016-01-07
dc.description.abstractUsing a recently developed recursive scheme for the calculation of high-order geometric derivatives of frequency-dependent molecular properties [Ringholm et al., J. Comp. Chem., 2014, 35, 622], we present the first analytic calculations of anharmonic infrared (IR) and Raman spectra including anharmonicity both in the vibrational frequencies and in the IR and Raman intensities. In the case of anharmonic corrections to the Raman intensities, this involves the calculation of fifth-order energy derivatives—that is, the third-order geometric derivatives of the frequency-dependent polarizability. The approach is applicable to both Hartree–Fock and Kohn–Sham density functional theory. Using generalized vibrational perturbation theory to second order, we have calculated the anharmonic infrared and Raman spectra of the non- and partially deuterated isotopomers of nitromethane, where the inclusion of anharmonic effects introduces combination and overtone bands that are observed in the experimental spectra. For the major features of the spectra, the inclusion of anharmonicities in the calculation of the vibrational frequencies is more important than anharmonic effects in the calculated infrared and Raman intensities. Using methanimine as a trial system, we demonstrate that the analytic approach avoids errors in the calculated spectra that may arise if numerical differentiation schemes are used.en_US
dc.description.sponsorshipThis work has received support from the Research Council of Norway through a Centre of Excellence Grant (Grant No. 179568/ V30) and a research grant (Grant No. 191251), the European Research Council through a ERC Starting Grant (Grant No. 279619), and from the Norwegian Supercomputer Program through a grant of computer time (Grant No. NN4654K).en_US
dc.descriptionPublished version. Source at <a href=http://doi.org/10.1039/c5cp06657c>http://doi.org/10.1039/c5cp06657c</a>. License <a href=https://creativecommons.org/licenses/by/3.0/>CC BY 3.0</a>.en_US
dc.identifier.citationCornaton Y, Ringholm M, Louant, Ruud K. Analytic calculations of anharmonic infrared and Raman vibrational spectra. Physical Chemistry, Chemical Physics - PCCP. 2016;18(5):4201-4215en_US
dc.identifier.issn1463-9076
dc.identifier.issn1463-9084
dc.identifier.otherFRIDAID 1431644
dc.identifier.other10.1039/c5cp06657c
dc.identifier.urihttps://hdl.handle.net/10037/10511
dc.language.isoengen_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.journalPhysical Chemistry, Chemical Physics - PCCP
dc.relation.projectIDNotur/NorStore: NN4654Ken_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN//191251/Norway///en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN//179568/Norway///en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/EC//279619/EU//en_US
dc.relation.urihttp://pubs.rsc.org/en/content/articlepdf/2016/cp/c5cp06657c
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.titleAnalytic calculations of anharmonic infrared and Raman vibrational spectraen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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