• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.453-459
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• 2013

In phtosynthetic light harvesting complexes, the electronic transition energies of chlorophylls are influenced by the Coulombic interaction with nearby molecules. Variation of the interactions caused by structural inhomogeneity in biological environment results in a distribution of disordered electronic transition energies of chlorophylls. In order to provide a practical guide to predict qualitative tendency of such distribution, we model four porphyrin derivatives including chlorophyll a molecule interacting with an external positive charge and calculate their transition energies using the time dependent density functional method. It is found that ${\pi}-{\pi}^*$ transition energies of the molecules are generally blue-shifted by the charge because this stabilizes occupied molecular orbitals to a greater extent than unoccupied ones. Furthermore, new transitions in the visible region emerge as a result of the red-shift in energy of an unoccupied Mg orbital and it is suggested that light-induced electron transfer may occur from the tetrapyrrole ring to the central magnesium when the molecules are interacting with a positive charge.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.22 no.9
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• pp.1217-1228
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• 1998

In order to elucidate the operational characteristics of rotating heat pipes, the internal flow patterns and heat transfer performance are investigated. Flow patterns and its transition are studied with various rotational speeds by visualizing flows established inside a rotating tube. To verify those results of analysis, 2 heat pipes of the same geometries but fill charge rates of 7, 30% were manufactured and submitted to operating tests. Comparison of experimental results on heat transfer rate show a fairly good agreement with the analytical results. The analysis reveals that the optimum charge ratio is ranged in 4~7% depending on the quantity of thermal loads. but the heat pipe with 7% of fill charge ratio reached dry-out limitation at heat flux of $q^{{\prime}{\prime}}=6.2kW/m^2$ lower than that of analytic results. Transition of flow regime was well related to the correlation by Semena & Khmelev on transient centrifugal Froude Number Frc. But hysteresis phenomenon was observed in transition of flow regime, when the rotational speed was stepwisely changed in the way to undergo 1 cycle.

• Journal of the Korean Electrochemical Society
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• v.12 no.3
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• pp.234-238
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• 2009

In the excitation spectra of $YNbO_4$ : $Eu^{3+}$, the charge transfer (CT) band around 270 nm due to $[NbO_4]^{3-}$$-Eu^{3+}$ interaction and sharp excitation peaks by f-f transition of $Eu^{3+}$ strongly appeared simultaneously. CT band depended on the structural properties of powders, showing the red-shift with increasing the crystallinity, while the f-f transition peaks were independent of the crystallinity. For $YNb_{1-x}Ta_xO_4$ : $Eu^{3+}$ (x = 0.05.0.2), $[TaO_4]^{3-}$. configuration was locally constructed, leading to the blue-shift in CT band and the decrease in the red emission intensity with increasing the Ta content.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1061-1065
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• 1996

The charge transfer compounds of tetrathiafulvalene (TTF) with the general formula of (TTF)mMCln, (M=Au, Pt, Ir, Os) were prepared by the direct reaction using excess HAuCl4·3H2O, H2PtCl6·xH2O, H2IrCl6·xH2O and H2OsCl6 respectively. The powdered electrical conductivities (σrt) at room temperature are given as follows; (TTF)3AuCl2, 4.53×10-3; (TTF)3.5AuCl2, 6.37×10-3; (TTF)3PtCl4, 5.51×10-4; (TTF)2IrCl4, 2.40×10-5; (TTF)OsCl4·1/2C2H5OH, 4.46×10-7 Scm-1. Magnetic susceptibility, electronic (UV-Vis.), vibrational (IR) and EPR spectroscopic evidences indicate that there is incomplete charge transfer from the TTF donor to gold, platinum, and iridium respectively, and that there is essentially complete charge transfer to osmium, thereby resulting a relatively low electrical conductivity in osmium compound. The EPR and magnetic susceptibility data reflect that the metals are in diamagnetic Au(Ⅰ), Pt(Ⅱ), Ir(Ⅲ), and Os(Ⅱ) oxidation states, and the odd electrons are extensively delocalized over the TTF lattices in each compound.

• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1269-1276
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• 1999

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

• JSTS:Journal of Semiconductor Technology and Science
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• v.12 no.3
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• pp.353-359
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• 2012

A highly efficient charge pump that minimizes the reverse charge sharing current (in short, reverse current) is proposed. The charge pump employs auxiliary capacitors and diode-connected MOSFET along with an early clock to drive the charge transfer switches; this new method provides better isolation between stages. As a result, the amount of reverse current is reduced greatly and the clock driver can be designed with reduced transition slope. As a proof of the concept, a 1.1V-to-9.8 V charge pump was designed in a $0.35{\mu}m$ 18 V CMOS technology. The proposed architecture shows 1.6 V ~ 3.5 V higher output voltage compared with the previously reported architecture.

• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.167-171
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• 1988

Formation of intermolecular charge-transfer complexes between 7,7,8,8-tetracyanoquinodimethane (TCNQ) and two different series of stilbene derivatives has been studied spectroscopically at $25^{\circ}$C in 1,2-dichloroethane. The compounds of Series I include stilbene and derivatives which have fused phenyl rings on one end of the central ethylene structure and a phenyl ring on the other end. The other Series, II, is comprised of stilbenes which have various para substituents on one of the two phenyl rings. The equilibrium constant, $K_c^{AD}$ and the molar extinction coefficient, ${\varepsilon}_{\lambda}^{AD}$, were determined using the Scott equation. The values of the charge-transfer transition frequency, ${\vu}_AD$ and $K_c{AD}$ correlated well respectively with the ionization potentials of the fused rings of Series Ⅰ or of the compounds of Series II and with the values of ${\sigma}_p$, the Hammett constants of the Series II substituents. trans-4-N,N-Dimethylaminostilbene and trans-4-nitrostilbene were found to be able to participate in electron transfer reaction with TCNQ forming the corresponding anion radical, TCNQ$^-$:

• 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.

• Journal of the Korean Magnetics Society
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• v.21 no.2
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• pp.56-60
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• 2011

Optical properties of $T_{0.2}Fe_{2.8}O_4$ (T = V, Cr, Mn) thin films derived from ferrimagnetic $Fe_3O_4$ were investigated by spectroscopic ellipsometry in the 1~8 eV photon-energy range. The difference in optical-absorption spectrum between the ternary compounds and $Fe_3O_4$ was analyzed based on preferable sites in spinel structure and iconicity of the doped V, Cr, and Mn ions. The observed absorption spectra from $Fe_3O_4$ and the ternary compounds can be interpreted as mainly due to charge-transfer transitions of Fe d electrons characterized by absorption structures with wide energy width. Also, the observed absorption structures with narrow energy width can be interpreted as due to crystal-field transitions between different d electron configurations of tetrahedral $Fe^{3+}(d^5)$ ion. The transitions were described in terms of spin-polarized electronic states of $Fe_3O_4$.

• Bulletin of the Korean Chemical Society
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• v.28 no.9
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• pp.1573-1578
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• 2007

Fluorescence quenching of norfloxacin (NOR) by Cu2+, Ni2+, Co2+ and Mn2+ was studied in water. The change in the fluorescence intensity and lifetime was measured as a function of quencher concentration at various temperatures. According to the Stern-Volmer plots, the NOR was quenched both by collisions and complex formation with the same quencher. However, the static quenching had a more important effect on the emission. Large static and dynamic quenching constants support significant ion-dipole and orbital-orbital interactions between NOR and cations. The both quenching constants by Cu2+ were the largest among quenchers. Also, quenching mechanism of Cu2+ was somewhat different. The change in the absorption spectra due to the quencher provided information on static quenching. The fluorescence of NOR was relatively insensitive to both the dynamic and static quenching compared with other quinolone antibiotics. This property can be explained by the twisted intramolecular charge transfer.