Modeling photoelectron spectra of conjugated oligomers with time-dependent density functional theory

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dc.citation.epage11007en_US
dc.citation.issueNumber41en_US
dc.citation.spage10997en_US
dc.citation.volumeNumber114en_US
dc.contributor.authorSalzner, U.en_US
dc.date.accessioned2016-02-08T09:56:27Z
dc.date.available2016-02-08T09:56:27Z
dc.date.issued2010en_US
dc.departmentDepartment of Chemistryen_US
dc.description.abstractWith the aim of producing accurate band structures of conjugated systems by employing the states of cations, TDDFT calculations on conjugated oligomer radical cations of thiophene, furan, and pyrrole with one to eight rings were carried out. Benchmarking of density functional theory and ab initio methods on the thiophene monomer shows that the ΔSCF ionization potential (IP) is most accurate at the B3LYP/6-311G* level. Improvement of the basis set beyond 6-311G* leads to no further changes. The IP is closer to experiment at B3LYP/6-311G* than at CCSD(T)/CCPVQZ. For longer oligomers the ΔSCF IPs decrease too fast with increasing chain length with all density functionals. CCSD/6-311G* performs well if the geometries are optimized at the CCSD level. With MP2 geometries IPs decrease too fast. Peak positions in photoelectron spectra were determined by adding appropriate TDDFT excitation energies of radical cations to the ΔSCF IPs. The agreement with experiment and with Green function calculations shows that TDDFT excited states of radical cations at the B3LYP/6-311G* level are very accurate and that absorption energies can be employed to predict photoelectron spectra.en_US
dc.identifier.doi10.1021/jp105588nen_US
dc.identifier.eissn1520-5215
dc.identifier.issn1089-5639
dc.identifier.urihttp://hdl.handle.net/11693/22171
dc.language.isoEnglishen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/jp105588nen_US
dc.source.titleJournal of Physical Chemistry Aen_US
dc.subjectAb initio methoden_US
dc.subjectAbsorption energiesen_US
dc.subjectBasis setsen_US
dc.subjectCCSDen_US
dc.subjectConjugated oligomeren_US
dc.subjectConjugated systemsen_US
dc.subjectDensity functionalsen_US
dc.subjectGreen functionen_US
dc.subjectPeak positionen_US
dc.subjectPhotoelectron spectrumen_US
dc.subjectRadical cationsen_US
dc.subjectThiophene monomersen_US
dc.subjectTime dependent density functional theoryen_US
dc.subjectIonization potentialen_US
dc.subjectOligomersen_US
dc.subjectOrganic polymersen_US
dc.subjectPhotoelectron spectroscopyen_US
dc.subjectPhotoelectronsen_US
dc.subjectPhotonsen_US
dc.subjectPositive ionsen_US
dc.subjectThiopheneen_US
dc.subjectDensity functional theoryen_US
dc.titleModeling photoelectron spectra of conjugated oligomers with time-dependent density functional theoryen_US
dc.typeArticleen_US

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