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Effect of matrix and substituent on the electronic structure of trapped benzene radical cations
Karpov Inst. of Physical Chemistry, Vorontsovo Pole Str. 10, Moscow 103064, Russian Federation, Inst. of Synth. Polymeric Materials, Russian Academy of Sciences, Profsoyuznaya Str. 70, Moscow 117393, Russian Federation.
Karpov Inst. of Physical Chemistry, Vorontsovo Pole Str. 10, Moscow 103064, Russian Federation.
Inst. of Synth. Polymeric Materials, Russian Academy of Sciences, Profsoyuznaya Str. 70, Moscow 117393, Russian Federation.
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2000 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 2, no 1, 29-35 p.Article in journal (Refereed) Published
Abstract [en]

The structure and dynamics of the radical cations produced from benzene, monodeuterated benzene and toluene in various low-temperature matrices were characterized by EPR and ENDOR spectroscopy. It was found that the nature of the matrix had a dramatic effect on the EPR spectra of benzene cation. Rigid structures corresponding to the 2B(1g) and 2B(2g) states are revealed in solid argon and halocarbon (CFCl3) matrices, respectively, whereas only dynamically averaged patterns are observed in other hosts used (krypton, xenon, sulfur hexafluoride). Deuterium monosubstitution has no appreciable effect on the cation structure observed in argon and halocarbon matrices, which implies matrix control of the preferred electronic state. In contrast, the toluene radical cation exhibits only a 2B(2g)-like structure both in argon and in CFCl3 matrices, that is, the internal structural effect strongly predominates over environment effects in this case. The results are discussed in qualitative terms taking into consideration the matrix and substituent effects on the charge distribution in benzene cation.

Place, publisher, year, edition, pages
2000. Vol. 2, no 1, 29-35 p.
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Engineering and Technology
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URN: urn:nbn:se:liu:diva-47727DOI: 10.1039/a906483dOAI: oai:DiVA.org:liu-47727DiVA: diva2:268623
Available from: 2009-10-11 Created: 2009-10-11 Last updated: 2017-12-13

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Lund, Anders

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