• Title/Summary/Keyword: time-resolved spectroscopic method

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The Application of Time-Resolved Laser Induced Fluorescence Spectroscopy in the Complexation Studies of Eu(III) and Cm(III) with Humic Substances

  • Joong Gill Choi;Oum Ka Won;Chang Yeoul Choi;Hichung Moon;Hyun Sang Shin;Park, Seung Min;Paul Joe Chong
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.72-78
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    • 1993
  • The application of time-resolved laser induced fluorescence spectroscopy (TRLIF) to the complexation studies of Eu(III) and Cm(III) with humic substances is described. Using this method, three different spectroscopic characteristics(excitation spectra, emission spectra, and lifetimes) of these aquo ions and their complexes can be directly measured. By observing shifts in the wavelength and changes in the lifetime and intensities of the fluorescence emission, the information on the complexation behavior of humic substances with these trivalent metal cations in an aqueous solution, as well as energy transfer mechanisms, can be obtained. In addition, this method allows precise spectroscopic quantification of the complexation processes at very low concentrations of both components.

Radial Speed of Current Sheath in Pulsed Discharge Plasma Device (펄스형 방전플라스마 장치에서 반경방향 Current Sheath의 속력)

  • Choi, Woon Sang;Jang, Jun Kyu
    • Journal of Korean Ophthalmic Optics Society
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    • v.13 no.3
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    • pp.57-60
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    • 2008
  • Purpose: The radial speed of plasma current sheath was measured at the plasma focus apparatus. Methods: The measurement was used to time-resolved spectroscopic method and Rogowski coils. Results: Radial current sheath speed was measured with $10^5$ cm/s at Helium and Argon pressure between 5 to 100 torr and discharging voltage of 15 kV. When the gas pressure was increased, the current sheath speeds were decreased. Conclusions: At the optimum condition of plasma focus apparatus, the radial speed is guessed $10^7$ cm/s as a results of the measurement of current sheath speed.

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Resolution of a Multi-Step Electron Transfer Reaction by Time Resolved Impedance Measurements: Sulfur Reduction in Nonaqueous Media

  • Park, Jin-Bum;Chang, Byoung-Yong;Yoo, Jung-Suk;Hong, Sung-Young;Park, Su-Moon
    • Bulletin of the Korean Chemical Society
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    • v.28 no.9
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    • pp.1523-1530
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    • 2007
  • The first reduction peak of the cyclic voltammogram (CV) for sulfur reduction in dimethyl sulfoxide has been studied using time resolved Fourier transform electrochemical impedance spectroscopic (FTEIS) analysis of small potential step chronoamperometric currents. The FTEIS analysis results reveal that the impedance signals obtained during short potential steps can be resolved into electron transfer reactions of two different time constants in a high frequency region. The FTEIS method provides snap shots of impedance profiles during an earlier phase of the reaction, leading to time resolved EIS measurements. Our results obtained by the FTEIS analysis are consistent with a series of electron transfer and chemical equilibrium steps of a complex reaction, making up an ECE (electrochemical-chemical-electrochemical) mechanism postulated from the results of computer simulation.

Direct Time-domain Phase Correction of Dual-comb Interferograms for Comb-resolved Spectroscopy

  • Lee, Joohyung
    • Current Optics and Photonics
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    • v.5 no.3
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    • pp.289-297
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    • 2021
  • We describe a comb-mode resolving spectroscopic technique by direct time-domain phase correction of unstable interferograms obtained from loosely locked two femtosecond lasers. A low-cost continuous wave laser and conventional repetition rate stabilization method were exploited for locking carrier and envelope phase of interferograms, respectively. We intentionally set the servo control at low bandwidth, resulting in severe interferograms' fluctuation to demonstrate the capability of the proposed correction method. The envelope phase of each interferogram was estimated by a quadratic fit of carrier peaks to correct timing fluctuation of interferograms in the time domain. After envelope phase correction on individual interferograms, we successfully demonstrated 1 Hz linewidth of RF comb-mode over 200 GHz optical spectral-bandwidth with 10-times signal-to-noise ratio (SNR) enhancement compared to the spectrum without correction. Besides, the group delay difference between two femtosecond pulses is successfully estimated through a linear slope of phase information.

Photo-induced inter-protein interaction changes in the time domain; a blue light sensor protein PixD

  • Terazima, Masahide
    • Rapid Communication in Photoscience
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    • v.4 no.1
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    • pp.1-8
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    • 2015
  • For understanding molecular mechanisms of photochemical reactions, in particular reactions of proteins with biological functions, it is important to elucidate both the initial reactions from the photoexcited states and the series of subsequent chemical reactions, e.g., conformation, intermolecular interactions (hydrogen bonding, hydrophobic interactions), and inter-protein interactions (oligomer formation, dissociation reactions). Although time-resolved detection of such dynamics is essential, these dynamics have been very difficult to track by traditional spectroscopic techniques. Here, relatively new approaches for probing the dynamics of protein photochemical reactions using time-resolved transient grating (TG) are reviewed. By using this method, a variety of spectrally silent dynamics can be detected and such data provide a valuable description about the reaction scheme. Herein, a blue light sensor protein TePixD is the exemplar. The initial photochemistry for TePixD occurs around the chromophore and is detected readily by light absorption, but subsequent reactions are spectrally silent. The TG experiments revealed conformational changes and changes in inter-protein interactions, which are essential for TePixD function. The TG experiments also showed the importance of fluctuations of the intermediates as the driving force of the reaction. This technique is complementary to optical absorption detection methods. The TG signal contains a variety of unique information, which is difficult to obtain by other methods. The advantages and methods for signal analyses are described in detail in this review.

Fluorescence Spectroscopic and Time-Dependent Density-Functional Theory Studies of Diphenylsilane

  • Boo, Bong-Hyun;Lee, Jae-Kwang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.993-996
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    • 2012
  • We investigated fluorescence and fluorescence excitation of diphenylsilane (DPS) in a solution and molecular beams in combination with the aid of the DFT method. When the molecule was photoexcited at 250 nm in a cyclohexane solution, normal and excimer fluorescences were observed in the ranges of 260-320 and 330-450 nm, respectively. The fluorescence excitation spectrum indicates that the channel leading to the intramolecular excimer formation is not efficient in comparison with the normal fluorescence. Vibrationally resolved fluorescence excitation spectra were measured for the DPS molecules cooled in pulsed supersonic expansion of He in the range 262.2-271.7 nm, in which we can see several electronic excitation spectra exhibiting the electronic band origins. We found that the simulated absorption spectrum based on the time-dependent densityfunctional theory calculations accords well with the absorption spectrum.

Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy

  • Kim, Hyeong-Mook;Park, Jaeheung;Noh, Hee Chang;Lim, Manho;Chung, Young Keun;Kang, Youn K.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.587-596
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    • 2014
  • A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

Fabrication of Transient Absorption Spectroscopic System and Measurement of Transient Absorption Changes of DDI (순간흡수 분광학 측정장치 구성 및 DDI의 순간흡수율 변화 측정)

  • Seo, Jung-Chul;Lee, Min-Yung;Kim, Dong-Ho;Jeong, Hong-Sik;Park, Seung-Han;Kim, Ung
    • Korean Journal of Optics and Photonics
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    • v.2 no.4
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    • pp.209-213
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    • 1991
  • Recently, the developments in generating and amplifying ultrashort optical pulses $(ps=10^{-12}s or fs=10^{-15}s)$ have imposed on great advances in the time-resolved laser spectroscopy. Especially, the transient absorption spectroscopy has a wide application range and the main idea of this technique is pump & probe method. After the pump pulse makes the material an excited or a transient states, the probe pulse is sent through the material to measure the absorbance change due to the transient states. Here, if the absorbance change was measured by the time delay between pump & probe pulses, the dynamic information of the excited or the transient states (the transient abnsorption changes by time & wavelength) can be obtained. At our laboratory, the ultrashort optic1 pulse (

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