Electronic Transitions of C6H4+ Isomers: Neon Matrix and Theoretical Studies

Fulara, Jan and Nagy, Adam and Filipkowski, Karol and Thimmakondu, Venkatesan S. and Stanton, John F. and Maier, John P.. (2013) Electronic Transitions of C6H4+ Isomers: Neon Matrix and Theoretical Studies. The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, and general theory, Vol. 117, H. 50 , S. 13605–13615.

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Official URL: http://edoc.unibas.ch/dok/A6211852

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Three open-chain isomers of C6H4+ and two cyclic ones were detected following mass-selective trapping in 6 K neon matrixes. The open-chain cations 5-hexene-1,3-diyne (CH2═CH–CC–CC–H)+ and cis- (cis-HCC–CH═CH–CCH)+ and trans-3-hexene-1,5-diyne (trans-HCC–CH═CH–CCH)+, possess two absorption systems commencing at 609 and 373, 622 and 385, and 585 and 373 nm, respectively. They are assigned to the 1 2A″ and 2 2A″ ← X̃ 2A″, 12A2 and 2 2A2 ← X̃ 2B1, and 1 2Bg and 2 2Bg ← X̃ 2Au electronic transitions of these cations. Two overlapping systems are detected at around 420 nm and tentatively assigned to the 1 2A″ ← X̃ 2A″ electronic transitions of propargyl cyclopropene and 2 2B1 ← X̃ 2A2 of o-benzyne cation structures. The assignment of the electronic transitions is based on theoretical vertical excitation energies calculated with CASPT2 and EOMEE-CCSDT methods for 12 isomers of C6H4+. These have been carried out at the geometries optimized using several ab initio methods. Adiabatic excitation energies were calculated for the five identified isomers of C6H4+.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Physikalische Chemie (Maier)
UniBasel Contributors:Maier, John Paul and Fulara, Jan and Filipkowski, Karol
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:31 Jan 2014 09:50
Deposited On:31 Jan 2014 09:50

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