DFT calculation of core- and valence-shell electron excitation and ionization energies of 2,1,3-benzothiadiazole C6H4SN2, 1,3,2,4-benzodithiadiazine C6H4S2N2, and 1,3,5,2,4-benzotrithiadiazepine C6H4S3N2

dc.creatorTakahata, Y
dc.creatorChong, DP
dc.date2012
dc.dateNOV
dc.date2014-07-30T14:42:16Z
dc.date2015-11-26T16:43:59Z
dc.date2014-07-30T14:42:16Z
dc.date2015-11-26T16:43:59Z
dc.date.accessioned2018-03-28T23:29:10Z
dc.date.available2018-03-28T23:29:10Z
dc.identifierJournal Of Electron Spectroscopy And Related Phenomena. Elsevier Science Bv, v. 185, n. 11, n. 475, n. 485, 2012.
dc.identifier0368-2048
dc.identifierWOS:000314439900007
dc.identifier10.1016/j.elspec.2012.09.015
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/61651
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/61651
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1273766
dc.descriptionThe vertical core and valence shell electron excitation and ionization energies of the three title molecules, 1-3, were calculated by density functional theory (DFT) using adequate functional for each type of processes and atoms under study. The inner shells treated were C1s, N1s, S1s, S2s, S2p. Molecular geometry was optimized by DFT B3LYP/6-311 + (d,p). The basis set of triple zeta plus polarization (TZP) Slater-type orbitals was employed for DFT calculations. The Delta SCF method was used to calculate ionization energies. The average absolute deviation (AAD) from experiment of 26 valence-electron ionization energies calculated by DFT for the three molecules 1-3 was 0.14 eV; while that of 24 calculated core-electron binding energies (CEBEs) from experiment was 0.4 eV. Selected core excitation energies were calculated by the multiplet approximation for the three molecules. The AAD of twelve calculated core excitation energies by the multiplet approximation that exclude S2s cases was 0.56 eV. Time-dependent DFT (TDDFT) was employed to calculate the excitation energies and corresponding oscillator strengths of core- and valence-electrons of the molecules. Some selected occupied core orbitals were used to calculate the core-excitation energies with the TDDFT (Sterner-Frozoni-Simone scheme). The core excitation energies thus calculated were in an average error of ca. 28 eV compared to observed values. They were shifted to the value calculated by the multiplet approximation. Convoluted spectra based upon the shifted energies and accompanying oscillator strengths reproduce low-energy region of observed spectra reasonably well, whereas they deviate from experiment in high-energy region. Reasonable agreement between theory and experiment was obtained for the valence electron excitations of the molecules. (C) 2012 Elsevier B.V. All rights reserved.
dc.description185
dc.description11
dc.description475
dc.description485
dc.descriptionNatural Sciences and Engineering Research Council (NSERC) of Canada
dc.descriptionFundacao de Amparo a Pesquisa do Estado do Amazonas-FAPEAM of State of Amazonas
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationJournal Of Electron Spectroscopy And Related Phenomena
dc.relationJ. Electron Spectrosc. Relat. Phenom.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectC6H4SxNy
dc.subjectCore electron
dc.subjectValence electron
dc.subjectIonization energy
dc.subjectExcitation energy
dc.subjectDensity functional theory
dc.subjectExact Exchange
dc.subjectDensity
dc.subjectApproximation
dc.subjectSpectra
dc.subjectModel
dc.titleDFT calculation of core- and valence-shell electron excitation and ionization energies of 2,1,3-benzothiadiazole C6H4SN2, 1,3,2,4-benzodithiadiazine C6H4S2N2, and 1,3,5,2,4-benzotrithiadiazepine C6H4S3N2
dc.typeArtículos de revistas


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