• Title/Summary/Keyword: Vibronic transition

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Characteristics of the Low Frequency Sequence Bands Observed in the Vibronic Emission Spectra of the Jet Cooled p-Fluorobenzyl Radical in the $D-1\rightarrow D_0$ Transition

  • 백대열;이상국
    • Bulletin of the Korean Chemical Society
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    • v.19 no.12
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    • pp.1359-1363
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    • 1998
  • The p-fluorobenzyl radical was generated from the p-fluorotoluene and vibronically excited in a corona excited supersonic expansion with inert buffer gases. The vibronic emission spectra of the jet cooled p-fluorobenzyl radical in the D1 → D0 transition have been observed in the visible region. The spectra exhibit several low frequency sequence bands in the vicinity of the every strong vibronic band. The characteristics of the sequence bands have been examined by varying the experimental conditions such as carrier gas and nozzle size to identify the origin of the transition in the spectra.

Vibronic Assignments of Isomeric Trimethylbenzyl Radicals : Revisited

  • Yi, Eun Hye;Yoon, Young Wook;Lee, Sang Kuk
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.737-742
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    • 2014
  • The vibronic emission spectra of isomeric trimethylbenzyl radicals were reassigned based on substituent effect on electronic transition energy as well as ab initio calculation of the benzyl radical. The electronic transition energy of three isomeric jet-cooled trimethylbenzyl radicals produced by corona discharge of 1,2,3,5-tetramethylbenzene were analyzed using the empirical data of three isomeric methylbenzyl radicals. Calculated data were obtained by summing up the shifts measured from methylbenzyl radicals as well as taking the position and alignment of substituents on the benzene ring into account. The revised assignments show better agreement with observation, and rationalize the validity of the model developed to explain the substituent effect on electronic transition energy of benzyl radicals.

Rotational Contour Analysis of the Vibronic Bands in the High Resolution Emission Spectra of the Benzyl Radical

  • 최익순;한명선;이상국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.10
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    • pp.882-885
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    • 1996
  • The 6a10 and 6b10 vibronic bands in the 12A2-12B2 electronic transition of the emission spectra of the benzyl radical obtained using a high resolution Fourier transform spectrometer are rotationally analyzed. The observed rotational contours were fitted by computer simulated rotational contours, providing determination of the variations, ΔA, ΔB, and ΔC of the rotational constants accompanying the vibronic transitions corresponding to each band. The molecular rotational constants A, B, and C are revised for the upper state and for the two lower states, respectively.

Spectroscopic Identification of Isomeric Trimethylbenzyl Radicals Generated from 1,2,3,4-Tetramethylbenzene

  • Yoon, Young-Wook;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2751-2755
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    • 2011
  • The visible vibronic emission spectrum was recorded from the corona discharge of precursor 1,2,3,4-tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion. The spectrum showed a series of vibronic bands in the $D_1{\rightarrow}D_0$ electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals, were produced as a result of removal of a hydrogen atom from the methyl group at different substitution positions. For each isomeric product, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state.

Analysis of Rotationally Cooled Vibronic Emission Spectra ($1^2A_2→1^2B_2$) of m-Xylyl Radical

  • 최익순;이상국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.8
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    • pp.749-753
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    • 1996
  • The rotationally cooled but electronically excited m-xylyl radical has been generated in a jet from the gas mixture of precursor m-xylene and buffer gas He by a technique of corona excited supersonic expansion. The visible vibronic emission spectra in the transition of 12A2→12B2 of m-xylyl radical in the gas phase have been recorded using a Fourier transform spectrometer. The spectra have been analyzed for the assignments of the vibrational frequencies in the electronic ground state with combination of the torsional frequencies reported previously.

Assignment of Vibronic Emission Spectra of Jet-Cooled m-Tolunitrile

  • Park, Chan Ho;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1377-1380
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    • 2006
  • The technique of corona-excited supersonic expansion was applied to produce electronically excited but rovibrationally cooled m-tolunitrile. The well-resolved vibronic emission spectrum of the jet-cooled m-tolunitrile in the $S_1\;\rightarrow \;S_0$ transition was recorded in the uv region using a Fourier transform spectrometer equipped with a Quartz-uv beam splitter. From an analysis of the spectrum observed, it was confirmed that the electronic transition and vibrational mode frequencies in the ground electronic state were accurately determined.

Rotationally Cooled Emission Spectra of p-Xylyl Radical

  • 최익순;이상국
    • Bulletin of the Korean Chemical Society
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    • v.16 no.11
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    • pp.1089-1093
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    • 1995
  • The p-xylyl radical has been produced in a jet from the precursor p-xylene with a corona excited supersonic expansion. Rotationally cooled vibronic emission spectra in the transition of 12A2→12B2 of the p-xylyl radical have been recorded using a Fourier transform spectrometer. The spectra were analyzed on the basis of the known vibrational frequencies and the bandshapes given by the rotational selection rules.

Vibronic Spectroscopy of Jet-Cooled Benzyl-type Radicals Produced from 2-Fluoro-4-Chlorotoluene by Corona Discharge

  • Chae, Sang Youl;Yoon, Young Wook;Lee, Sang Kuk
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3565-3569
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    • 2013
  • A home-made pinhole-type glass nozzle was employed to generate vibronically excited but jet-cooled benzyl-type radicals from precursor 2-fluoro-4-chlorotoluene with a large amount of carrier gas He, from which the visible vibronic emission spectrum was recorded with a long-path monochromator. From an analysis of the spectrum observed, it was found that two benzyl-type radicals, 2-fluorobenzyl and 2-fluoro-4-chlorobenzyl radicals, were formed from the precursor in corona discharge. The possible pathway for the production of benzyl-type radicals that can explain the spectroscopic observation is herein proposed. In addition, the electronic energy of the $D_1{\rightarrow}D_0$ transition and the vibrational mode frequencies in the $D_0$ state of the 2-fluoro-4-chlorobenzyl radical were determined for the first time.