Other
Scientific paper
Jun 2011
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confetd11s&link_type=abstract
"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec
Other
Electronic
Scientific paper
In recent years it has been proposed that resonance-stabilized radicals (RSRs) may play an important role as intermediates in the formation of polycyclic aromatic hydrocarbons (PAHs). RSRs gain extra stability by delocalizing the unpaired electron through a neighboring conjugated π-system. Because of this extra stability, RSRs are able to build up in concentration, allowing for the creation of larger, more complex systems through their recombination with other RSRs. Mass-selective two-color resonant two-photon ionization spectra of two RSRs, phenylallyl and benzylallenyl radicals, have been recorded under jet-cooled conditions. These two radicals, while sharing the same radical conjugation, have unique properties. The phenylallyl and benzylallenyl radicals were respectively produced via discharge of trans-β-methylstyrene and benzylallene in argon prior to supersonic expansion. The D0-D1 origin of the phenylallyl radical was found at 19204 wn and was found to have a strong vertical ionization energy of 6.905(2) eV. By comparison, the benzylallenyl radical has an origin at 19703 wn and, while showing similar Franck-Condon activity to phenylallyl, has an IP curve indicative of a large geometry change between the ground state and the ion 7.50(2) eV. Visible-visible holeburning was used to show that each radical exists in one conformeric form in the expansion. The CH stretch region of each radical was taken using D0-Resonant Ion Dip Infrared Spectroscopy in a novel four laser experiment. A combination of this and DFT calculations was used to show that each radical exists in a trans geometry.
Buchanan Evan
Kidwell Nathan
Sebree Joshua A.
Zgierski Marek
Zwier Timothy S.
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