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 Title: Vibronic Emission Spectroscopy Of Benzyl-type Radicals Generated By Corona Discharge Author(s): Lee, Sang Contributor(s): Yoon, Young; Yi, Eun Hye Subject(s): Radicals Abstract: Benzyl radical is a prototypical aromatic free radical and has been the subject of numerous spectroscopic studies. On the other hand, ring-substituted benzyl radicals, benzyl-type radicals, have received less attention due to the difficulties associated with production in corona discharge and analysis of spectra. We report vibronic emission spectra of hetero halogen multi-substituted benzyl radicals generated by corona discharge of corresponding toluene derivatives using a pinhole-type glass nozzle, from which visible vibronic emission spectra were recorded using a long-path monochromator. The spectra show nice features of strongest origin band and a series of vibronic bands in the lower energies originating from the vibrationless D$_1$ state. From the analysis of the spectra observed, we determined the energies of the D$_1$ $\rightarrow$ D$_0$ electronic transition and vibrational mode frequencies in the ground electronic state.\footnote{Y.~W.~Yoon and S.~K.~Lee, \textit{J.~Phys.~Chem.~A} \underline{\textbf{117}}, 2485 (2013).} On the other hand, all substituted benzyl radicals show the origin bands shifted to red region with respect to the parental benzyl radical at 22002 cm$^{-1}$. The shifts of multi-substituted benzyl radicals can be well estimated using the method developed from mono-substituted benzyl radicals as well as the positions of nodal point and mutual orientation of substituents, which could be useful for scientists to set a proper scanning range of their spectrometers for the spectroscopic observation of transient molecules. In this presentation, we will discuss the substituent effect\footnote{Y.~W.~Yoon, S.~Y.~Chae, and S.~K.~Lee, \textit{Chem.~Phys.~Lett.} \underline{\textbf{584}}, 37 (2013).}\footnote{Y.~W.~Yoon and S.~K.~Lee, \textit{Chem.~Phys.~Lett.} \underline{\textbf{570}}, 29 (2013).}on electronic transition energy and the experimental technique developed in this laboratory. Issue Date: 2014-06-16 Publisher: International Symposium on Molecular Spectroscopy Citation Info: Lee, S.; Yoon, Y.; Yi, E.H. VIBRONIC EMISSION SPECTROSCOPY OF BENZYL-TYPE RADICALS GENERATED BY CORONA DISCHARGE. Proceedings of the International Symposium on Molecular Spectroscopy, Urbana, IL, June 16-21, 2014. DOI: 10.15278/isms.2014.MI01 Genre: CONFERENCE PAPER/PRESENTATION Type: Text Language: English URI: http://hdl.handle.net/2142/51145 DOI: 10.15278/isms.2014.MI01 Rights Information: Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/ Date Available in IDEALS: 2014-09-172015-04-14
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