• Title/Summary/Keyword: Vibrational Spectroscopy

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Vanadyl Binary Schiff Base Complexes Containing N2O2 Coordination Sphere: Synthesis, Ab Initio Calculations and Thermodynamic Properties

  • Asadi, Mozaffar;Ghatee, Mohammad Hadi;Torabi, Susan;Mohammadi, Khosro;Moosavi, Fatemeh
    • Journal of the Korean Chemical Society
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    • v.57 no.1
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    • pp.63-72
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    • 2013
  • Some vanadyl complexes were synthesized by treating a methanolic solution of the appropriate Schiff base ligand and one equivalent of $VO(SO_4)_2$ to yield [($VOL_2^{1-14}$)](L=Salicylaldehyde's derivatives, Schemes 1, 2). These oxovanadium (IV) complexes were characterized based on their FT-IR, UV-Vis spectroscopy and elemental analysis. The IR spectra suggest that coordination takes place through azomethine nitrogen and phenolate oxygen. In addition, the formation constants of the oxovanadium (IV) binary complexes were determined in methanolic medium. The ab initio calculations were also carried out to determine the structural and the geometrical properties of one of the complexes and its calculated vibrational frequencies were investigated.

SERS Analysis of CMC on Gold-Assembled Micelle

  • Jang, Nak-Han
    • Bulletin of the Korean Chemical Society
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    • v.25 no.9
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    • pp.1392-1396
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    • 2004
  • The micellization of dodecylpyridinum chloride (DPC) assembled on aqueous gold nanoparticles has been studied as a function of concentration using Surface-Enhanced Raman Scattering (SERS). At the low concentration, the strong SERS band of the benzene ring moiety was observed at 1025 $cm^{-1}$, and assigned to “trigonal ring breathing”. According to high concentration of DPC, a new strong band was also appeared at 1012 $cm^{-1}$, which was assigned to “totally symmetry ring breathing”. The difference of two spectra seems to ascribe to the geometry of polar head group, i.e., pyridinium cation. These geometry exist flat-down at low concentration, whereas standing-up or tilted geometry at high concentration. The critical micelle concentration (CMC) was first obtained from the ratio of intensities of the two bands related to the benzene ring moiety by vibrational spectroscopy, and was about 28 mM. After the CMC, the benzene ring moiety in the micelle state was more restricted than in monomer state because there is no more change of intensities at 1012 $cm^{-1}$. In addition, the size of gold-assembled micelle was estimated using light scattering and it was about 328.3 nm.

Application of 532 nm YAG-Laser Annealing to Crystallization of Amorphous Si Thin Films Deposited on Glass Substrates

  • Lee, Jong-Won;So, Byung-Soo;Chung, Ha-Seung;Hwang, Jin-Ha
    • Korean Journal of Materials Research
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    • v.18 no.3
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    • pp.113-116
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    • 2008
  • A 532 nm Nd-YAG laser was applied to crystallize amorphous Si thin films in order to evaluate the applicability of a Nd-YAG laser to low-temperature polycrystalline Si technology. The irradiation of a green laser was controlled during the crystallization of amorphous Si thin films deposited onto glass substrates in a sophisticated process. Raman spectroscopy and UV-Visible spectrophotometry were employed to quantify the degree of crystallization in the Si thin films in terms of its optical transmission and vibrational characteristics. The effectiveness of the Nd-YAG laser is suggested as a feasible alternative that is capable of crystallizing the amorphous Si thin films.

Inelastic Electron Tunneling Spectroscopy of 1-layer Arachidicacid films using a Polyimide barrier (Polyimide 터널 장벽을 이용한 Arachidicacid 단분자막의 비탄성 터널 스펙트라)

  • Lee, Won-Jae;Kang, Dou-Yol;Iwamoto, Mitsumasa
    • Proceedings of the KIEE Conference
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    • 1994.11a
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    • pp.234-236
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    • 1994
  • We fabricated Au/PI/Pb and Au/PI/1-layer Arachidic acid/Pb structures in order to electron transport properties through the junctions. It was found that 9-layer PI LB films function as a good tunneling barrier from the I-V properties. And several peaks originating in the vibrational modes of the constituent molecules of 1-layer arachidicacid LB films were clearly observed in $d^2V/dI^2-V$ curves.

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Electronic Spectroscopy and Ligand Field Analysis of mer-[Cr(progly)(2,2-tri)]$CIO_4$

  • Park, Jong-Ha
    • Journal of Photoscience
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    • v.9 no.3
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    • pp.51-55
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    • 2002
  • The 77 K emission and excitation spectra, and 298 K infrared and absorption spectra of [Cr(progly)(2,2-tri)]CIO$_4$[progly=prolylglycinate,2,2-tri=N-(2-aminoethyl)-1,2-ethanediamine] have been measured. The vibrational intervals of the electronic ground state are extracted from emission and infrared spectra. The twelve electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed electronic transitions, a ligand field analysis was performed to determine the metaligand bonding properties for the coordinated atoms. It is found that the carboxylate oxygen of the progly is a strong $\sigma$-and $\pi$-donor while the peptide nitrogen has weak $\pi$-donor property toward chromium(III) ion.

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The Adsorption Energetics and Geometry of Ketene Physisorbed on Ag(111)$^*$

  • Kim, Jeong Su;Dae, Hye Ryeong
    • Bulletin of the Korean Chemical Society
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    • v.16 no.2
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    • pp.143-148
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    • 1995
  • Ketene (CH2CO) adsorption on Ag(111) has been studied in ultrahigh vacuum using electron energy loss spectroscopy and temperature programmed desorption. Ketene adsorbs molecularly on Ag(111) at temperatures below 126 K. The coverage increases linearly with exposure until saturation. No multilayer formation and no shift in desorption temperature with coverage were observed, indicating a lack of attractive interaction between adsorbate molecules. The desorption activation energy is estimated to be 7.8 kcal/mol by assuming first order kinetics and a pre-exponential factor of 1013 sec-1. The adsorption geometry of ketene on the surface is determined from the relative intensities of the vibrational energy loss peaks. The CCO axis of CH2CO is found to be almost parallel to (∼4°away from) the surface and the molecular plane is almost perpendicular to the surface (∼3°tilt).

Configuration Interaction Theory and van der Waals Predissociation

  • 이천우
    • Bulletin of the Korean Chemical Society
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    • v.16 no.9
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    • pp.850-858
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    • 1995
  • Golden-rule like formulas have been used without theoretical basis to calculate the resonance lifetimes and final state distributions in the predissociation of van der Waals molecules. Here we present their theoretical basis by extending Fano's configuration interaction theory. Such extensions were independently done by Farnonux [Phys. Rev. 1985, 25, 287] but his work, unfortunately, was not well known outside some small group of people in the field of Auger spectroscopy. Since my extension is easier to understand than his, it is presented here. Theoretical basis of Golden rule like formulas used in the predissociation of van der Waals molecules was obtained by using such extensions. Factors responsible for several aspects of predissociation dynamics, such as variations of dynamics as functions of resonance lifetimes, or variations in shapes of final quantum state distributions of photofragments around resonances, were identified. Parameters, or dynamical information that could be obtained from the measurement of partial cross section spectra were accordingly determined. The theory was applied to the vibrational predissociation of triatomic van der Waals molecules and its result was compared with those calculated by close-coupling method. An example where Golden-rule like expression fails and branching ratios vary greatly around a resonance was considered.

High Resolution Optical Spectroscopy of mer-[Cr(dpt)(Gly-Gly)]ClO₄

  • 최종하
    • Bulletin of the Korean Chemical Society
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    • v.20 no.4
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    • pp.436-440
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    • 1999
  • The highly resolved absorption spectra of mer-[Cr(dpt)(Gly-Gly)]ClO4·H2O [dpt = di(3-aminopropyl)amine, H2Gly-Gly = glycylglycine] have been measured between 13000 cm-1 and 50000 cm-1 temperatures down to 2 K. The vibrational intervals were extracted by recording emission and far-infrared spectra. The characteristic infrared bands in meridional isomer were discussed. The four-teen electronic origins due to spin-allowed and spin-forbidden transitions were assigned. With the use of this electronic transitions, a ligand field optimization based on the exact known ligand geometry have been performed to determine more detailed bonding properties of Gly-Gly and dpt ligands. It is confirmed that the peptide nitrogen of the Gly-Gly has a weak π-donor property toward chrornium(Ⅲ) ion.

Dopping Effect of Fluorine Atom on the Superconductivity of $YBa_2Cu_3O_{7-x}F_y$

  • Kim, Keu-Hong;Cho, Seun- Koo;Kim, Yoo-Young;Park, Jong-Sik;Choi, Mu-Yong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.5
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    • pp.460-463
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    • 1990
  • The normal and fluorinated high-Tc superconducting materials, $YBa_2Cu_3O_{7-x}F_y$with $0.25{\leq}x{\leq}0.55\;and\;0.00{\leq}y{\leq}0.30$, were synthesized to investigate the dopping effect of fluorine atom on the superconductivity of Y123 and studied by X-ray diffraction analysis and electron probe microanalysis, resistivity and thermopower measurements, and polarized micro-Raman spectroscopy. The reproducible micro-Raman spectra were recorded and analyzed. The coherent assignments could be suggested for the spectra of normal and fluorinated samples. The fluorine atoms introduced were found to be substituted for oxygen in pyramidal Cu-O units rather than in Cu-O chains. The unit cell parameters were decreased upon the substitution of oxygen by fluorine atom. From the decreasing cell parameters and Tc, the increasing thermopower, and the possible assignments of the vibrational modes, it could be suggested that the dopping of fluorine atom localizes the superconducting electrons in Y123.

The Role of Vibrational Coherency in Ultrafast Reaction Dynamics of PYP

  • Chosrowjan, Haik;Mataga, Noboru;Taniguchi, Seiji;Shibata, Yutaka;Hamada, Norio;Tokunaga, Fumio;Imamoto, Yasushi;Kataoka, Mikio
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.122-125
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    • 2002
  • Coherent oscillations in is fluorescence dynamics of W.-t. PYP and its site-directed mutants have been observed. Two oscillatory modes coupled with the ultrafast fluorescence due to the twisting of the excited chromophore were identified, a high ftequency mode (∼135 cm$\^$-1/) with ∼550 is damping time and a low frequency overdamped mode (-45 cm$\^$-1/) with ∼250 is damping time, respectively. Both modes disappear in the fluorescence dynamics of denatured PYP emphasizing the important role of the protein nanospace as the environment for photoreaction. The qualitative picture of fluorescence dynamics in site-directed mutants was rather similar to that in W.-t. PYP, i.e., similar oscillatory modes (∼130-140 cm$\^$-1/ and ∼40-70 cm$\^$-1/) have been observed. This indicates that the vibrational modes and electron-vibration couplings do not change dramatically due to the mutation though the damping time of low frequency mode a little decreases as the protein nanospace structure becomes looser and more disordered by mutation. On the other hand, in the case of some PYP analogues, the qualitative picture of fluorescence dynamics changes, showing the familiar picture of solvation effect whereas the oscillations are almost damped. Comparative analyses of these observations are presented.

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