• Journal of the Korean Graphic Arts Communication Society
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• v.11 no.1
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• pp.17-29
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• 1993

As inverstigating the influence of monomers and photoinitiator in the polymerization rate of photopolymerization by using IR spectroscopy, photopolymerizations initiated by ultraviolet radiation are characterized by the presence of an autoacceleration in the polymerization rate as the reaction proceeds. The conversion for the end of the autoacceleration varies considerably depending on the monomer and reaction condition which determines coil size and viscosity. In UV curable systems, the autoacceleration begins at only a few percent conversion and continues to 40% in HEA solution and 60% conversion in EHA solution. The polymerization ate in HEA solution increased as follow; DMHA > HCPK > DMPA and could be explained by the interaction between the initiating radical and HEA monomer and the size of the photodissociated radical of initiator. But the tendency of autoacceleration in EHA solution is almost independent on initiator.

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.62-68
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• 1980

Ultraviolet spectrophotometric investigations have been carried out the systems of monoalkylbenzene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes. The equilibrium constants for these complexes of representative monosubstituted benzene reveal the following order of increasing stability: benzene < methyl- < ethyl- < n-propyl-benzene. The value of ${\Delta}H$, ${\Delta}G$, and ${\Delta}S$ for interaction of a number of monoalkyl substituted benzene with iodine has been determinated. In general, as ΛH becomes increasingly negative, corresponding decreases in ${\Delta}G$ and ${\Delta}S$ values are observed, and these variation are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.740-743
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• 1993

By considering both electron-electron and electron-lattice interactions, the effect of charge transfer on the bond structure and electronic states of $C_{60}$ is studied without configuration limitation. The results show that the electron-electron interaction does not eliminate the layer structure of the bond distortion and the self-trapping of transferred electrons. For charged ${C_{60}}^{2-}$, there exist two localized electronic states, which possess laminar wave functions, and four nonequivalent groups of carbon atoms, which induce a fine-structure in the NMR spectrum line.

• Bulletin of the Korean Chemical Society
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• v.7 no.3
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• pp.186-190
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• 1986

Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.3-15
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• 1992

Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, $(CO)_5Cr=CCHCH_2(XCH_3)\;,\;(CO)_5Mo=CCHCH_2(XCH_3)\;, and\;(CO)_5W=CCHCH_2(XCH_3)$, are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The ${\sigma}$ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the $(CO)_5M$. The ${\pi}$ bond is formed through the back-transfer of electrons from one of the degenerated d${\pi}$ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.59-59
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• 2010

Graphene is a 2-D sheet of $sp^2$-bonded carbon arranged in a honeycomb lattice. This material has attracted major interest, and there are many ongoing efforts in developing graphene devices because of its high charge mobility and crystal quality. Therefore clear understanding of the substrate effect and mechanism of synthesis of graphene is important for potential applications and device fabrication of graphene. In a published paper in J. Phys. Chem. C (2008), the effect of substrate on the atomic/electronic structures of graphene is negligible for graphene made by mechanical cleavage. However, nobody shows the interaction between Ni substrate and graphene. Therefore, we have studied this interaction. In order to studying these effect between graphene and Ni substrate, We have observed graphene synthesized on Ni substrate and graphene transferred on $SiO_2$/Si substrate through Raman spectroscopy. Because Raman spectroscopy has historically been used to probe structural and electronic characteristics of graphite materials, providing useful information on the defects (D-band), in-plane vibration of sp2 carbon atoms (G-band), as well as the stacking orders (2D-band), we selected this as analysis tool. In our study, we could not observe the doping effect between graphene and Ni substrate or between graphene and $SiO_2$/Si substrate because the shift of G band in Raman spectrum was not occurred by charge transfer. We could noticed that the bonding force between graphene and Ni substrate is more strong than Van de Waals force which is the interaction between graphene and $SiO_2$/Si. Furthermore, the synthesized graphene on Ni substrate was in compressive strain. This phenomenon was observed by 2D band blue-shift in Raman spectrum. And, we consider that the graphene is incommensurate growth with Ni polycrystalline substrate.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.313-325
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• 2007

In order to have better insights into adsorption of organic molecules on kaolinite surfaces, we performed quantum chemical calculations of interaction between three different model clusters of kaolinite siloxane surfaces and benzyl alcohol, with emphasis on the effect of size and lattice topology of the cluster on the variation of electron density and magnetic shielding tensor. Model cluster 1 is an ideal silicate tetrahedral surface that consists of 7 hexagonal rings, and model cluster 2 is composed of 7 ditrigonal siloxane rings with crystallographically distinct basal oxygen atoms in the cluster, and finally model cluster 3 has both tetrahedral and octahedral layers. The Mulliken charge analysis shows that siloxane surface of model cluster 3 undergoes the largest electron density transfer after the benzyl alcohol adsorption and that of model cluster 1 is apparently larger than that of model cluster 2. The difference of Mulliken charges of basal oxygen atoms before and after the adsorption is positively correlated with hydrogen bond strength. NMR chemical shielding tensor calculation of clusters without benryl alcohol shows that three different basal oxygen atoms (O3, O4, and O5) in model cluster 2 have the isotropic magnetic shielding tensor as $228.2{\pm}3.9,\;228.9{\pm}3.4,\;and\;222.3{\pm}3.0ppm$, respectively. After the adsorption, the difference of isotropic chemical shift varies from 1 to 5.5 ppm fer model cluster 1 and 2 while model cluster 2 apparently shows larger changes in isotropic chemical shift. The chemical shift of oxygen atoms is also positively correlated with electron density transfer. The current results show that the adsorption of benzyl alcohol on the kaolinite siloxane surfaces can largely be dominated by a weak hydrogen bonding and electrostatic force (charge-charge interaction) and demonstrate the importance of the cluster site and the lattice topology of surfaces on the adsorption behavior of the organic molecules on clay surfaces.

• Applied Chemistry for Engineering
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• v.2 no.4
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• pp.311-329
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• 1991

Electrochemical behavior of surface active Osmium bipyridine complex adsorbed in a monomolecular layer on tin oxide electrodes by the Langmuir-Blodgett method was studied. Theoretical equation of cyclic voltammetry of electrode reactions for redox species adsorbed as monolayer form was discussed by reversible and quasi-reversible waves. The film was transferred onto the $SnO_2$ electrode surface and then amounts of charge on the electrode were measured in the technique of cyclic voltammetry. The electron transfer mediation of these monolayer with $Fe^{2+}$, TEMPOL and others were studied. And the cyclic voltammetry were simulated by taking into account the interaction parameters. From these values, we found it possible to fit almost all measured cyclic voltammograms with these parameters. The recent works and directions using LB method were introduced with various applicable field.

• Journal of the Korean Chemical Society
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• v.39 no.5
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• pp.338-343
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• 1995

The electronic structure of photoskinsensitizing 8-azapsoralen and 4,4',5'-trimethyl-8-azapsoralen has been investigated by the semiempirical (PM3-CI-UHF, etc) methods. The formation of molecular complexes between ground thymine and excited azapsoralen is discussed in terms of charge transfer interaction. The results indicated that the most probable orientation through C4-cycloaddition of 3,4-double bond of azapsoralen and 5,6-double bond of thymine bases, expecially photoadducts were inferred to be a trans-anti azapsoralen(3,4) < > Thymine(5,6) and trans-anti 4,4',5'-trimethyl-8-azapsoralen (3,4) < > Thymine(5,6).

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3671-3676
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• 2013

A series of carbon nanotube, $C_{60}$, and graphene modified $TiO_2$ nanocomposites were prepared by hydrothermal method. X-ray diffraction, $N_2$ adsorption, UV-Vis spectroscopy, photoluminescence, and Electrochemical impedance spectra were used to characterize the prepared composite materials The results reveal that incorporating $TiO_2$ with carbon materials can extend the adsorption edge of all the $TiO_2$-carbon nanocomposites to the visible light region. The photocatalytic activities were tested in the degradation of 2,4,6-trichlorophenol (TCP) under visible light. No obvious difference in essence was observed in structural and optical properties among three series of carbon modified $TiO_2$ nanocomposites. Three series of carbon materials modified $TiO_2$ composites follow the analogous tentative reaction mechanism for TCP degradation. GR modified $TiO_2$ nanocomposite exhibits the strongest interaction and the most effective interfacial charge transfer among three carbon materials, thus shows the highest electron-hole separation rate, leading to the highest photocatalytic activity and stability.