Performance of Density Functional Theory in Computing Nonresonant Vibrational (Hyper)Polarizabilities
dc.contributor.author
dc.date.accessioned
2019-07-10T07:49:30Z
dc.date.available
2019-07-10T07:49:31Z
dc.date.issued
2013-07-30
dc.identifier.issn
0192-8651
dc.identifier.uri
dc.description.abstract
A set of exchange-correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM-B3LYP, LC-BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of alltrans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the M ller-Plesset second-order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM-B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity-dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro-optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field-induced second harmonic generation all of them, as well as the Hartree-Fock approximation, yield the wrong sign. We have also found that the Pople 6-311G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry
dc.format.extent
10 p.
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application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1002/jcc.23316
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© Journal of Computational Chemistry, 2013, vol. 34, núm. 20, p. 1775-1784
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Articles publicats (D-Q)
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Tots els drets reservats
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Bulik, Ireneusz W. Zaleśny, Robert Bartkowiak, Wojciech Luis Luis, Josep Maria Kirtman, Bernard Scuseria, Gustavo E. Avramopoulos, Aggelos Reis, Heribert Papadopoulos, Manthos G. 2013 Performance of Density Functional Theory in Computing Nonresonant Vibrational (Hyper)Polarizabilities Journal of Computational Chemistry 34 20 1775 1784
dc.subject
dc.title
Performance of Density Functional Theory in Computing Nonresonant Vibrational (Hyper)Polarizabilities
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
018588
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1096-987X