• Title/Summary/Keyword: Vibronic spectrum

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Spectroscopic Identification of Isomeric 2,3- and 2,6-Dimethylbenzyl Radicals in Corona Discharge

  • Yoon, Young Wook;Lee, Sang Kuk
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.763-767
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    • 2013
  • We resolved the controversial assignments of the visible vibronic bands observed from corona discharge of 1,2,3-trimethylbenzene. The vibronic bands belonging to the jet-cooled 2,6-dimethylbenzyl radical were clearly identified from the spectrum observed from corona discharge of 2,6-dimethylbenzyl chloride. After subtracting the bands of the 2,6-isomer from the spectrum observed from corona discharge of 1,2,3-trimethylbenzene, the vibronic bands of the 2,3-isomer were also identified. By comparing data with the known vibrational data of 1,2,3-trimethylbenzene and the results of ab initio calculations, we determined the electronic energies of the $D_1{\rightarrow}D_0$ transitions and vibrational mode frequencies in the ground electronic states of the 2,3-and 2,6-dimethylbenzyl radicals.

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.

Vibronic Assignments of the $S_1 \rightarrow S_0$ Emission Spectrum of the Jet Cooled p-Fluorotoluene

  • 하영미;최익순;이상국
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.202-206
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    • 1998
  • The p-fluorotoluene was vibronically excited in a jet with a buffer gas He in a corona excited supersonic expansion. The vibronic emission spectrum of the jet cooled p-fluorotoluene in the transition of S1 → S0 has been recorded with a Fourier transform spectrometer in the uv region. The spectrum observed was analyzed to obtain accurate vibrational frequencies in the ground electronic state by comparing with those reported previously. The origin of the low frequency sequence bands observed in this work was discussed. Also, the absence of significant intensity of hot band resulting from the excited vibrational states in the spectrum suggests extensive vibrational cooling in the source.

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.

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.

Spectroscopic Evidence of Jet-Cooled p-Chloro-α-Methylbenzyl Radical in Corona Excitation

  • Huh, Chang-Soon;Yoon, Young-Wook;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.33 no.9
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    • pp.2943-2948
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    • 2012
  • We report the first spectroscopic evidence of the jet-cooled p-chloro-${\alpha}$-methylbenzyl radical. The visible vibronic emission spectrum was recorded from the corona discharge of precursor p-chloro-ethylbenzene seeded in a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with a technique of corona excited supersonic expansion. From the comparison with the vibronic spectrum of the p-chlorobenzyl radical, we identified the evidence of formation of the jet-cooled p-chloro-${\alpha}$-methylbenzyl radical in the corona discharge of precursor p-chloro-ethylbenzene.

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.

Evidence of Molecular Rearrangement in Benzyl-type Radicals

  • Yoon, Young-Wook;Lee, Seung-Woon;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2783-2785
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    • 2010
  • Searching for new molecular radicals which are believed to play an important role as reaction intermediates in aromatic chain reactions, we have applied the technique of corona excited supersonic expansion employing a pinhole-type glass nozzle to obtain the vibronic spectrum from the corona discharge of precursor 3,5-difluorotoluene with a large amount of inert carrier gas helium. An analysis of the observed spectrum revealed that many vibronic bands are from other isomeric difluorobenzyl radicals generated in the jet by migration of the fluorine atom or methylene group to the adjacent position in the 3,5-difluorobenzyl radical. A possible mechanism was proposed for the formation of other isomers by using a bridged cyclic intermediate structure.

Flourescence characteristics of the Alexandrite Laser (Alexandrite 레이저의 형광특성)

  • 윤태현
    • Proceedings of the Optical Society of Korea Conference
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    • 1990.02a
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    • pp.26-28
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    • 1990
  • Cw arc 램프로 펌핑하는 Alexandrite 레이저의 형광을 optical Spectrum Analyzer를 이용하여 측정하였다. Vibronic 천이에 해당하는 광대역 형광 스펙트럼이 관측되었고, arc 램프 입력에 따른 peak 형광의 세기 및 peak intensity 파장의 입력 power 의존성을 조사하였다. 형광의 세기는 입력 power에 따라 0.16 /kw의 비율로 증가하였고, peak intensity 파장은 입력 power가 5kw 까지는 5 nm/kw 비율로 장파장쪽으로 이동하였다.

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