• 제목/요약/키워드: vibrational spectroscopy

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Electronic Spectroscopy and Structure of CLF

  • Vadim A. Alekseev;D. W. Setser
    • Bulletin of the Korean Chemical Society
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    • 제21권1호
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    • pp.9-22
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    • 2000
  • Optical-optical double resonance experiments have been used to identify and characterize five ion-pair states and several of the bound and repulsive valence states of ClF. This report provides a description of these experiments for $^{35}CIF$ and $^{37}CIF$, and a summary of the current knowledge of the valence and ion-pair states. The important role of perturbations among the rovibronic levels of the bound valence states and their utilization in the double resonance technique is discussed. The ion-pair states of the same symmetry, ${\Omega}$=$0^+$ (E and f) and 1( $\beta$ and G) interact very strongly and the spectroscopy of these states is anomalous and, hence, interesting. Comparison is made to some recent ab initio calculations for ClF. One possible explanation of the irregular vibrational energy levels and rotational constants of the ion-pair states of $O^+$ and 1 symmetry is a crossing of the diabatic potentials of these states. Some currently unresolved questions about ClF spectroscopy are posed for future work. Where appropriate, analogy is made between the electronic states of ClF and the corresponding valence and ion-pair states of $Cl_2.$.

Picosecond Photoionization Processes of N,N,N',N'-Tetramethyl-p-phenylenediamine (TMPD) in Water

  • Lee, Min-Yung;Jang, Du-Jeon;Kim, Dong-Ho;Lee, Sun-Sook;Boo, Bong-Hyun
    • Bulletin of the Korean Chemical Society
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    • 제13권1호
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    • pp.17-20
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    • 1992
  • Photoionization processes of TMPD in $H_2O$ and $D_2O$ were studied, by measuring steady-state absorption, emission, fluorescence excitation spectra, and fluorescence lifetimes on picosecond time scale. The steady-state absorption spectra showed that there exists a cation-ion pair (Wurster's Blue) in $H_2O$ and in $D_2O$ in the electronic ground state. Temperature and excitation wavelength dependence were also studied and the results show that the photoionization reaction in water is an activated process and the fluorescence lifetime is independent of the vibrational excess energy in the uv excitation range of 283-310 nm.

Raman Spectroscopy of Irradiated Normoxic Polymethacrylic Acid Gel Dosimeter

  • Bong, Ji-Hye;Choi, Kyu-Seok;Yu, Soo-Chang;Kwon, Soo-Il;Cho, Yu-Ra;Park, Chae-Hee;Park, Hyung-Wook
    • Bulletin of the Korean Chemical Society
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    • 제32권2호
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    • pp.625-629
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    • 2011
  • A quantitative analysis of the decreasing rate of the monomer and increasing rate of the polymerization was made by monitoring radiation level increments using Raman spectroscopy within the therapeutic radiation range for a normoxic polymethacrylic acid gel dosimeter. The gel dosimeter was synthesized by stirring materials such as gelatin, distilled water, methacrylic acid, hydroquinone and tetrakis phosphonium chloride at $50^{\circ}C$, and the synthesized gel was contained in a 10- mm diameter and 32-mm high vial to conduct measurement. 24 hours after gel synthesis, it was irradiated from 0 Gy to 20 Gy by 2 Gy using a Co-60 radiotherapy unit. With use of the Cryo FE-SEM, structural changes in the 0 Gy and 10 Gy gel dosimeters were investigated. The Raman spectra were acquired using 532-nm laser as the excitation source. In accordance with fitting the changes in C-COOH stretching (801 $cm^{-1}$), C=C stretching (1639 $cm^{-1}$) and vinyl $CH_2$ stretching (3114 $cm^{-1}$) vibrational modes for monomer and $CH_2$ bending vibrational mode (1451 $cm^{-1}$) for polymer, sensitive parameter S for each mode was calculated. The values of S for monomer bands and polymer band were ranged in $6.0{\pm}2.6$ Gy and $7.2{\pm}2.3$ Gy, respectively, which shows a relatively good conformity of the decreasing rate of monomer and the increasing rate of polymerization within the range of error.

Guided Wave THz Spectroscopy of Explosive Materials

  • Yoo, Byung-Hwa;Kang, Seung-Beom;Kwak, Min-Hwan;Kim, Sung-Il;Kim, Tae-Yong;Ryu, Han-Cheol;Jun, Dong-Suk;Paek, Mun-Cheol;Kang, Kwang-Yong;Chung, Dong-Chul
    • Journal of electromagnetic engineering and science
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    • 제11권1호
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    • pp.42-50
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    • 2011
  • One of the important applications of THz time-domain spectroscopy (TDS) is the detection of explosive materials through identification of vibrational fingerprint spectra. Most recent THz spectroscopic measurements have been made using pellet samples, where disorder effects contribute to line broadening, which results in the merging of individual resonances into relatively broad absorption features. To address this issue, we used the technique of parallel plate waveguide (PPWG) THz-TDS to achieve sensitive characterization of three explosive materials: TNT, RDX, and HMX. The measurement method for PPWG THz-TDS used well-established ultrafast optoelectronic techniques to generate and detect sub-picosecond THz pulses. All materials were characterized as powder layers in 112 ${\mu}m$ gaps in metal PPWG. To illustrate the PPWG THz-TDS method, we described our measurement by comparing the vibrational spectra of the materials, TNT, RDX, and HMX, applied as thin powder layers to a PPWG, or in conventional sample cell form, where all materials were placed in Teflon sample cells. The thin layer mass was estimated to be about 700 ${\mu}g$, whereas the mass in the sample cell was ~100 mg. In a laboratory environment, the absorption coefficient of an explosive material is essentially based on the mass of the material, which is given as: ${\alpha}({\omega})=[ln(I_R({\omega})/I_S({\omega}))]m$. In this paper, we show spectra of 3 different explosives from 0.2 to 2.4 THz measured using the PPWG THz-TDS.

Vibronic Emission Spectrum of Jet-Cooled o-Tolunitrile in a Corona Excited Supersonic Expansion

  • Park, Chan-Ho;Lee, Gi-Woo;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • 제27권6호
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    • pp.881-885
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    • 2006
  • We have employed a technique of corona excited supersonic expansion to generate electronically excited but jet-cooled o-tolunitrile. The vibronically well-resolved emission spectrum of the jet-cooled o-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. The electronic transition and vibrational mode frequencies in the ground electronic state were accurately determined from the analysis of the spectra observed.

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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    • 제27권9호
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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.

Interplay of the Intramolecular Water Vibrations and Hydrogen Bond in N-Methylacetamide-Water Complexes: Ab Initio Calculation Studies

  • Kim, Joo-Hee;Cho, Min-Haeng
    • Bulletin of the Korean Chemical Society
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    • 제24권8호
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    • pp.1061-1068
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    • 2003
  • The correlation between the water and N-methylacetamide (NMA) intramolecular vibrational frequencies and the hydrogen-bond length in a variety of NMA-H₂O and NMA-D₂O complexes was investigated by carrying out ab initio calculations. As the hydrogen-bond length decreases, the frequencies of bending and stretching modes of the hydrogen-bonding water increases and decreases, respectively, and the amide I and II (III) mode frequencies of the NMA decreases and increases, respectively. In this paper, correlation maps among the amide (I, II, and III) modes of NMA and three intramolecular water modes are thus established, which in turn can be used as guidelines for interpreting two-dimensional vibrational spectra of aqueous NMA solutions.

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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    • 제34권3호
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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.

F-Center Excitation Energy Transfer to CN$^-$ vibrational Levels in CsCl

  • Jang, Du-Jeon
    • 한국광학회:학술대회논문집
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    • 한국광학회 1990년도 광학 및 양자전자학 워크샵
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    • pp.94-100
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    • 1990
  • The rapid quenching dynamics of the F-center excitation by CN- defects in CsCl crystals were investigated by monitoring the ground state bleach recovery kinetics of F-centers, using a picosecond streak camera absorption spectrometer. The F-centers in CN- doped quenched samples show two bleach recovery components. Optical aggregation converts the slow component to the fast component. The slow one is due to the normal relaxation of the F*-centers as found in CN_ free crystals. The fast one is due to the energy transfer of the F-center electronic excitation to the vibrational energy levels of CN_ molecualr defects. The energy transfer occurs only in the F-center-CN_ defect pairs, FH(CN_)-centers.

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Photoemission and Excitation Spectroscopy of cis-Difluoro(1,4,8,11-Tetraazacyclotetradecane) Chromium (III) Perchlorate

  • Park, Jong-Ha;Hong, Yong-Pyo;Park, Yu-Chul;Ryoo, Keon-Sang
    • Journal of Photoscience
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    • 제7권1호
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    • pp.21-26
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    • 2000
  • The photoemission and excitation spectra of cis-[Cr(cyclam)F$_2$]ClO$_4$ (cyclam = 1,4,8,11-tetraazacy-clotetradecane) taken at 77 K are reported. The 298 K mid- and far-infrared spectra are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. The zero-phonon line In the excitation spectrum splits into two components by 169 cm$^{1}$, and the large $^2$E$_{g}$ splitting can be reproduced by the ligand field theory. According to the ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong c-donor character, and fluoride ligand also has strong $\sigma$- and $\pi$-donor properties toward chromium(III) ion.n.

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