• Title/Summary/Keyword: charge-transfer transition

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SPIN POLARIZED PHOTOEMISSION AND MAGNETIC CIRCULAY DICHROISM STUDY OF FeAl THIN FILMS

  • Kim, K.W.;Kudryavtsev, Y.V.;Chang, G.S.;Whang, C.N.;Lee, Y.P.
    • Journal of the Korean Vacuum Society
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    • v.6 no.S1
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    • pp.53-58
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    • 1997
  • It is well known that the equiatomic FeAl alloy crystallizes in a paramagnetic CsCl structure and is very stable in a wide temperature range owing to a significant charge transfer from Al to Fe. A presence of structural defects normally enhances the magnetic and magneto-optical properties of this alloy. In this study spin-resolved photoemission and magnetic circular dichroism (MCD) were carried out on both ordered and disordered $Fe_{0.52}Al_{0.48}$ alloy films. The disordered state in the alloy films was obtained by a vapor quenching deposition on cooled substrates. It is shown that the order-disorder transition in the Fe0.52Al0.48 alloy films leads to a significant change in the spin polarization. Form the MCD results the orbital and spin magnetic moments of the constituent atoms are obtained. According to the sum rule the spin and orbital magnetic moments of Fe in the disordered FeAl film are $\mu\frac{SR}{spin}=0.8\mu_B$ and $\mu\frac{SR}{orb}=0.14\mu_B$ respectively. The spin magnetic moment is also evaluated to be $\mu\frac{BR}{spin}=0.77\mu_B$ by the branching ration method employing a photon polarization of 90%.

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Dependence of Electronic Spectra on the Degree of Conjugation in Organocobalt(Ⅲ) Complexes (공액도에 따른 유기코발트 착화합물의 전자스펙트럼에 관한 연구)

  • Hye Kyung Seo;Chan Ah Bong;Young Ae Hwang Park
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.1047-1052
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    • 1993
  • The electronic spectra of enzyme-model organocobalt(Ⅲ) complexes containing completely or partially conjugated macrocyclic ligands were measured in various solvents to investigate the solvent effect on the charge transfer band for the axial cobalt-carbon bond by the extent of conjugation in the equatorial macrocyclic ring; completely conjugated, $CH_3CoL,\;C_6H_5CoL,\;CNCoL,\;CH_3CoL',\;CNCoL'$, partially conjugated $CH_3(py)Co(DH)_2, CH_3CoL"$, unconjugated dienes, $[CH_3Co(1,4-CT)](ClO_4)_2$, and open ring, $CH_3Co(salen)$. The position of the charge transfer band which corresponds to the cobalt-carbon bond was shifted to a shorter wavelength as the polarity of solvent increased and the transition energy $(E_T)$ had a linear relationship with solvent polarity parameter, Z-value, only in the case of completely conjugated system. However, the linear correlation between $E_T$and Z was not observed for partially conjugated and open ring systems.

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Structural and optical properties of Ni-substituted spinel $LiMn_2O_4$ thin films (니켈 치환된 스피넬 LiMn2O4 박막의 구조적, 광학적 성질)

  • Lee, Jung-Han;Kim, Kwang-Joo
    • Journal of the Korean Vacuum Society
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    • v.15 no.5
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    • pp.527-533
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    • 2006
  • Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

Synthesis and Characterization of Metal Complex Oxo Vanadium(Ⅳ) Complexes with Derivatives of Salicylaldoximes (옥심계 금속착물의 합성과 그 물성에 관한 연구 치환 살리실알데히드옥심의 바나듐(Ⅳ) 착물(1))

  • Lee, Kwang;Lee, Won Sik
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.611-616
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    • 1995
  • Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

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The Effect of Pressure on the Iododestannylation between Tetramethyltin and Iodine (Tetramethyltin과 Iodine 사이의 Iododestannylation에 대한 압력의 영향)

  • Kwun, Oh Cheun;Lee, Young Hoon;Jeun, In Seung
    • Journal of the Korean Chemical Society
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    • v.39 no.5
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    • pp.350-355
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    • 1995
  • UV spectrophotometric investigation has been carried out on the system of charge-transfer (CT) complex with iodine and tetramethyltin in carbon tetrachloride solvent. The transient CT absorption spectrum can be observed in ${\lambda}_{max}=270nm$ and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine (iododestannylation). From there, the rate constants for the iododestannylation were determined at 10, 20 and $35^{\circ}C$ up to 1200 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were obtained and from these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_F2$ mechanism and weakened $S_F2$ mechanism nature by increasing pressure.

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Visible Light-based Photocatalytic Degradation by Transition Metal Oxide (전이 금속 산화물을 이용한 가시광선 기반 광촉매 분해)

  • Lee, Soomin;Park, Yeji;Lee, Jae Hun;Patel, Rajkumar
    • Membrane Journal
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    • v.29 no.6
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    • pp.299-307
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    • 2019
  • Photocatalysis is an environment friendly technique for degrading organic dyes in water. Tungsten oxide is becoming an active area of research in photocatalysis nanomaterials for having a smaller bandgap than the previously favored titanium dioxide. Synthesis of hierarchical structures, doping platinum (Pt), coupling with nanocomposites or other semiconductors are investigated as valid methods of improving the photocatalytic degradation efficiency. These impact the reaction by creating a redshift in the wavelength of light used, effecting charge transfer, and the formation/recombination of electron-hole pairs. Each of the methods mentioned above are investigated in terms of synthesis and photocatalytic efficiency, with the simplest being modification on the morphology of tungsten oxide, since it does not need synthesis of other materials, and the most efficient in photocatalytic degradation being complex coupling of metal oxides and carbon composites. The photocatalysis technology can be incorporated with water purification membrane by modularization process and applied to advanced water treatment system.

The electronic structure of the ion-beam-mixed Pt-Cu alloys by XPS and XANES

  • Lim, K.Y.;Lee, Y.S.;Chung, Y.D.;Lee, K.M.;Jeon, Y.;Whang, C.N.
    • Proceedings of the Korean Vacuum Society Conference
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    • 1998.02a
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    • pp.133-133
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    • 1998
  • In the thin film alloy formation of the transition metals ion-beam-mixing technique forms a metastable structure which cannot be found in the arc-melted metal alloys. Sppecifically it is well known that the studies about the electronic structure of ion-beam-mixed alloys pprovide the useful information in understanding the metastable structures in the metal alloy. We studied the electronic change in the ion-beam-mixed ppt-Ct alloys by XppS and XANES. These analysis tools pprovide us information about the charge transfer in the valence band of intermetallic bonding. The multi-layered films were depposited on the SiO2 substrate by the sequential electron beam evapporation at a ppressure of less than 5$\times$10-7 Torr. These compprise of 4 ppairs of ppt and Cu layers where thicknesses of each layer were varied in order to change the alloy compposition. Ion-beam-mixing pprocess was carried out with 80 keV Ae+ ions with a dose of $1.5\times$ 1016 Ar+/cm2 at room tempperature. The core and valence level energy shift in these system were investigated by x-ray pphotoelectron sppectroscoppy(XppS) pphotoelectrons were excited by monochromatized Al K a(1486.6 eV) The ppass energy of the hemisppherical analyzer was 23.5 eV. Core-level binding energies were calibrated with the Fermi level edge. ppt L3-edge and Cu K-edge XANES sppectra were measured with the flourescence mode detector at the 3C1 beam line of the ppLS (ppohang light source). By using the change of White line(WL) area of the each metal sites and the core level shift we can obtain the information about the electrons pparticippating in the intermetallic bonding of the ion-beam-mixed alloys.

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The study on the spectroscopic and electrical properties of Azomethine compounds (Azomethine계 화합물의 분광학적 특성과 전기적 특성에 관한 연구)

  • Baek, Dae-Jin;Oh, Won-Chun;Ko, Young-Shin
    • Analytical Science and Technology
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    • v.8 no.3
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    • pp.249-258
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    • 1995
  • The polymers, polyazine, polyazomethine ( I ) and polyazomethine ( II ) were prepared by the condensation of p-benzoquinone with hydrazine hydrate, p-phenylenediamine and diaminomaleonitrile in DMSO, respectively. The IR spectra of these polymers showed a characteristic peak of schiff base (-C=N-) at about $1600cm^{-1}$. These polymers dissolved in concentrated sulfuric acid showed UV/VIS absorption near 300nm indicatiog the presence of iminium ion(>$C\limits^{\small\oplus}=NH-$). Another UV/VIS absorption band in the region of 350~415nm was shown presumably due to the charge transfer transition in the molecule. The electrical conductivities of polyazine, polyazomethine ( I ) and ( II ) were measured. The self-electrical conductivity of these was found to be about $10^{-14}{\sim}10^{-11}{\Omega}^{-1}cm^{-1}$ and these polymers doped with $I_2$ showed the maximum conductivity of about $10^{-2}{\Omega}^{-1}cm^{-1}$.

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Synthesis and Characterization of Molybdeum Complexes with Schiff-Bases(II), Dioxobis(N-aryl-3-methoxysalicyaldiminato) Molybdenum(VI) Complexes (몰리브덴의 시프-염기착물의 합성과 그 성질 (제2보). 다이옥소비스(질소-아릴-3-메톡시살리실알디미나토)몰리브데늄(VI) 착물)

  • O, Sang O;Gu, Bon Gwon
    • Journal of the Korean Chemical Society
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    • v.29 no.3
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    • pp.257-264
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    • 1985
  • Dioxobis(3-methoxysalicyaldehydato)molybdeum(VI) complex has been synthesized by reactions of 3-methoxysalicylaldehyde and ammonium paramolybdate in methanol solution. With appropriate primary amine, the resulting complex gave schiff-base complexes, MoO$_2$(CH$_3$O-sal-N-R)$_2$ in which C=O oxide ligands had been replaced by nitrogen. The properties and possible molecular structure of these complexes were discussed by elemental analysis, spectroscopic studies and electric conductivities measurements. It was found that the Mo(VI) complexes contain a cis-MoO$_2$ group since their infrared spectra two Mo=O band at about 900cm$^{-1}$ and the combining ratios for MoO$_2$-ligand are 1 : 2. Also, electronic spectra of molybdenyl complexes assigned to ligand-to-metal charge transfer transition. All of these complexes are yellow or orange, depolar compound and slightly soluble in alcohol, dichloromethane, chloroform and N,N-dimethylformamide.

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The Effect of Pressure on the $S_F2$ Cleavage Reaction of Tetramethyltin with Iodine (Tetramethyltin과 Iodine의 $S_F2$ 분해반응에 대한 압력의 영향)

  • Oh Cheun Kwun;Jin Burm Kyong;Young Hoon Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.3
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    • pp.287-293
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    • 1993
  • Ultraviolet spectrophotometric investigation has been carried out on the system of charge-transfer(CT) complex with iodine and tetramethyltin in n-hexane and acetone. From these results, the transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum is accompained by the cleavage of tetramethyltin with iodine (iododestannylation). Therefore, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the rates of reaction were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$) were obtained and discussed in terms of solvent structure variation of transition state and mechanism from these values. It could postulated that the reaction is followed with S$_F$2 mechanism and weakened S$_F$2 mechanism nature by increasing pressure.

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