Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene
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Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene

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Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene

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dc.contributor.author Serrano Andrés, Luis
dc.contributor.author Merchán Bonete, Manuela
dc.contributor.author Nebot Gil, Ignacio José
dc.contributor.author Lindh, Roland
dc.contributor.author Roos, Björn O.
dc.date.accessioned 2010-06-18T08:03:06Z
dc.date.available 2010-06-18T08:03:06Z
dc.date.issued 1993
dc.identifier.uri http://hdl.handle.net/10550/12988
dc.language.iso en en
dc.relation http://scitation.aip.org/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JCPSA6000098000004003151000001&idtype=cvips&prog=normal&doi=10.1063/1.465071 en
dc.source SERRANO ANDRÉS, Luis ; MERCHAN, Manuela ; NEBOT GIL, Ignacio ; LINDH, Roland ; ROOS, Björn, O. Towards an accurate molecular orbital theory for excited states: Ethene, butadiene, and hexatriene. En: Journal of Chemical Physics, 1993, vol. 98, no. 4 en
dc.subject Calculation Methods ; Quantum Chemistry ; Ab Initio Calculations ; Electron Spectra ; Butadiene ; Accuracy ; Scf Calculations ; Triplets ; Rydberg States ; Excitation ; Errors ; Polyenes ; Excited States en
dc.title Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene en
dc.type info:eu-repo/semantics/article en
dc.type info:eu-repo/semantics/publishedVersion en
dc.subject.unesco UNESCO::FÍSICA::Química física en
dc.identifier.doi 10.1063/1.465071 en
dc.description.abstractenglish A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic electron correlation effects are in a subsequent step added using second order perturbation theory with the CASSCF wave function as the reference state. The approach is here tested in a calculation of the valence and Rydberg excited singlet and triplet states of the title molecules, using extended atomic natural orbital (ANO) basis sets. The ethene calculations comprised the two valence states plus all singlet and triplet Rydberg states of 3s, 3p, and 3d character, with errors in computed excitation energies smaller than 0.13 eV in all cases except the V state, for which the vertical excitation energy was about 0.4 eV too large. The two lowest triplet states and nine singlet states were studied in butadiene. The largest error (0.37 eV) was found for the 2 1Bu state. The two lowest triplet and seven lowest singlet states in hexatriene had excitation energies in error with less than 0.17 eV. en
dc.description.private serrano@uv.es ; merchan@uv.es ; nebot@uv.es en

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