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dc.contributor.authorGao, Bin
dc.contributor.authorRingholm, Magnus
dc.contributor.authorBast, Radovan
dc.contributor.authorRuud, Kenneth
dc.contributor.authorThorvaldsen, Andreas johan
dc.contributor.authorJaszuński, Michał
dc.date.accessioned2015-02-25T09:48:48Z
dc.date.available2015-02-25T09:48:48Z
dc.date.issued2014-01-09
dc.description.abstractWe present a general approach for the analytic calculation of pure vibrational contributions to the molecular (hyper)polarizabilities at the density-functional level of theory. The analytic approach allows us to study large molecules, and we apply the new code to the study of the first dipole hyperpolarizabilities of retinal and related molecules. We investigate the importance of electron correlation as described by the B3LYP exchange–correlation functional on the pure vibrational and electronic hyperpolarizabilities, and compare the computed hyperpolarizabilities with available experimental data. The effects of electron correlation on the pure vibrational corrections vary signficantly even between these structurally very similar molecules, making it dif- ficult to estimate these effects without explicit calculations at the density-functional theory level. As expected, the frequency-dependent first hyperpolarizability, which determines the experimentally observed second-harmonic generation, is dominated by the electronic term, whereas for the static hyperpolarizability the vibrational contribution is equally important. As a consequence, frequency extrapolation of the measured optical hyperpolarizabilities can only provide an estimate for the electronic contribution to the static hyperpolarizability, not its total value. The relative values of the hyperpolarizabilities for different molecules, obtained from the calculations, are in reasonable agreement with experimental data.en
dc.identifier.citationJournal of Physical Chemistry A 118(2014) nr. 4 s. 748-756en_US
dc.identifier.cristinIDFRIDAID 1178913
dc.identifier.doi10.1021/jp408103y
dc.identifier.issn1089-5639
dc.identifier.urihttps://hdl.handle.net/10037/7207
dc.identifier.urnURN:NBN:no-uit_munin_6809
dc.language.isoengen_US
dc.publisherACS Publicationsen_US
dc.rights.accessRightsopenAccess
dc.subject444:Teoretisk kjemi, kvantekjemien_US
dc.subject444:Theoretical chemistry, quantum chemistryen_US
dc.subjectretinolen
dc.subjectretinoic aciden
dc.subjectvitamin A acetateen
dc.subjectretinal Schiff baseen
dc.subjectprotonated retinal Schiff baseen
dc.subjectsecond-harmonic generationen
dc.titleAnalytic density functional theory calculations of pure vibrational hyperpolarizabilities: The first dipole hyperpolarizability of retinal and related moleculesen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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