• Title/Summary/Keyword: donor-state

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OPTICAL SPECTROSCOPY AND LIGAND FIELD PARAMETERS OF CIS-DIBROMO(1,4,8,11-TETRAAZACYCLOTETRADECANE) CHROMIUM(III) BROMIDE

  • Choi, Jong-Ha
    • Journal of Photoscience
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    • v.4 no.3
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    • pp.121-125
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    • 1997
  • The 77 K emission and excitation, and room-temperature visible spectra of cis[Cr(cyclam)Br$_2$]Br (cyclam=1,4,8,11-tetraazacyclotetradecane) are reported. The mid- and far-infrared spectra at room-temperature 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. It is found that nitrogen atoms of the cyclam ligand have strong $\sigma$-donor characters, but bromide ligand has weak $\sigma$- and $\pi$-donor properties toward chromium(III) ion. The zerophonon line in the excitation spectrum splits into two components by 172 cm$^{2-}$, and the large $^2E_g$ splitting can be reproduced by the ligand field theory.

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Electronic and Vibrational Spectroscopy of cis-Diisothiocyanato(1,4,8,11-tetraazacyclotetradecane)chromium(Ⅲ) Thiocyanate

  • Choi, Jong-Ha;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.384-388
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    • 2003
  • The emission and excitation spectra of $cis-[Cr(cyclam)(NCS)_2]NCS$ (cyclam = 1,4,8,11-tetraazacyclotetradecane) taken at 77 K are reported. The infrared and visible spectra at room temperature are also measured. The vibrational intervals due to the electronic ground state are extracted from the far-infrared and emission spectra. The ten pure electronic origins due to spin-allowed and spin-forbidden transitions are assigned by analyzing the absorption and excitation spectra. Using the observed transitions, a ligand field analysis has been performed to determine the bonding properties of the coordinated ligands in the title chromium(Ⅲ) complex. According to the results, it is found that nitrogen atoms of the cyclam ligand have a strong σ-donor character, while the NCS ligand has medium σ- and π-donor properties toward chromium(Ⅲ) ion.

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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Triplet Excitation Energy Transfer as a Function of Concentration in Glassy Methylbenzophenone

  • 한형순;이재광;남계준;최용국;국성근
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.923-926
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    • 1998
  • Spectral diffusion following direct triplet excitation from the ground state in glassy Methylbenzophenone as a function of transition energy has been studied. The concentrations of donor and acceptor have been determined for different transition energies. The geometrical distribution was determined by a computer simulation. The cluster size increases gradually with concentration and cluster percolation is observed at 0.31 mole fraction for a three dimensional system. The average distance between a donor and an acceptor also has been determined for different concentrations. The energy transfer efficiency changes abruptly at a critical concentration of 0.054, corresponding to a critical distance of 9.8 Å. The γvalue was evaluated to be 1.17.

Theoretical Studies on the Gas-Phase Wolff Rearrangement of Ketocarbenes

  • 김찬경;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.395-401
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    • 1997
  • The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

Effects of Light Intensity on the Steady-State Fluorescence Quenching Kinetics

  • Mino Yang;Sangyoub Lee;Kook Joe Shin;Kwang Yul Choo;Duckhwan Lee
    • Bulletin of the Korean Chemical Society
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    • v.12 no.4
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    • pp.414-423
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    • 1991
  • Effects of light intensity on the steady-state fluorescence quenching kinetics are examined for general cases where the bimolecular quenching can occur via long-range energy transfer processes and the potential of mean force between the energy donor and acceptor molecules is not negligible. Approximate analytic expressions are derived for the steady-state quenching rate constant and for the ratio of the steady-state intensity of unquenched to quenched fluorescence. The analytic results are compared with the exact results obtained from numerical analysis and the results of conventional theories.

The Political Economy of Aid Failure in Zambia

  • Kim, Jiyoung
    • International Area Studies Review
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    • v.21 no.4
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    • pp.271-294
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    • 2017
  • Despite a huge amount of foreign assistance and close economic guidance by international donors throughout the past decades, Zambia today still suffer from a high level of aid dependency and the absence of sustainable economic development. In this study, I investigate the factors that resulted in aid (and development) failure in Zambia, focusing on institutional/historical contexts. I propose that in Zambia, government has largely failed to implement (or even produce) effective economic policies that could lead to successful use of foreign assistance for long-term, sustainable development. In particular, I focus on the nature of state and politics in Zambia, and argue that failed politics is one of the main causes of development and aid failure in Zambia and highlight colonial legacies and other contextual/institutional factors to understand the nature of politics and state in Zambia. In particular, this paper proposes that the Zambian case demonstrates that foreign aid and donor influence could worsen the situation directly by simply providing wrong guidance and also by further weakening the state (and institutional) capacity of the recipient country.

Technology of Decision-Making Support Regarding the Possibility of Donation and Transplantation Considering Civil Law

  • Hnatchuk, Yelyzaveta;Hovorushchenko, Tetiana;Drapak, Georgii;Kysil, Tetiana
    • International Journal of Computer Science & Network Security
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    • v.22 no.9
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    • pp.307-315
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    • 2022
  • The review of known decision-making support systems and technologies regarding the possibility of donation and transplantation showed that currently there are no systems and technologies of decision-making support regarding the possibility of donation and transplantation considering civil law. The paper models the decision-making support process regarding the possibility of donation and transplantation, which is a theoretical basis for the development of rules, methods and technology of decision-making support regarding the possibility of donation and transplantation considering civil law. The paper also developed the technology of decision-making support regarding the possibility of donation and transplantation considering civil law as a component of the Unified State Information System for Organ and Tissue Transplantation, which automatically and free of charge determines the possibility/impossibility of donation and transplantation. In the case of the possibility of donation, the admissible type of donation is also determined - over-life or after-life donation - and data about potential donor is entered in the relevant Donor Register. In the case of the possibility of transplantation, if the recipient needs a transplant of one of the paired organs or a part of the organ/tissue, then data about potential recipient are entered in the Transplantation List from both over-life and after-life donor, otherwise, if the recipient needs a transplant of a non-paired organ or both paired organs, then data about potential recipient are entered only in the Transplantation List from after-life donor.

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.

Effect of V$_2$O$_5$ Addition on Microwave Dielectric Properties of (Zr$_{0.8}$,Sn$_{0.2}$)TiO$_4$ (V$_2$O$_5$의 첨가가 (Zr$_{0.8}$,Sn$_{0.2}$)TiO$_4$의 마이크로파 유전특성에 미치는 영향)

  • 이경호
    • Journal of the Microelectronics and Packaging Society
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    • v.8 no.1
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    • pp.27-32
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    • 2001
  • The effect of $V_2O_5$, a donor-type dopant on the degradation of quality factor of ($Zr_{0.8}, Sn_{0.2})TiO_4$was compared with Ta$_2$O$_{5}$ doped ($Zr_{0.8}, Sn_{0.2})TiO_4$ in terms of microstructure, electrical conductivity, and oxidation state of the dopant. It is well known that the addition of the donor type species such as $Ta_2O_5,Nb_2O_5, Sb_2O_5, WO_{3}$, increases the quality factor of ($Zr_{0.8}, Sn_{0.2})TiO_4$due to decrease the oxygen vacancy concentration. Unlike other dopants, however, the addition of $V_2O_5$ decreased the quality factor. The degradation of quality factor of ($Zr_{0.8}, Sn_{0.2})TiO_4$was resulted from the formation of grain boundary phase and $V_2O_5$rich fiber shaped secondary phase, and the increasing the oxygen vacancy concentration due to unstability of oxidation state of vanadium ions in ($Zr_{0.8}, Sn_{0.2})TiO_4$ceramic.c.

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