• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.763-767
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• 2013

We resolved the controversial assignments of the visible vibronic bands observed from corona discharge of 1,2,3-trimethylbenzene. The vibronic bands belonging to the jet-cooled 2,6-dimethylbenzyl radical were clearly identified from the spectrum observed from corona discharge of 2,6-dimethylbenzyl chloride. After subtracting the bands of the 2,6-isomer from the spectrum observed from corona discharge of 1,2,3-trimethylbenzene, the vibronic bands of the 2,3-isomer were also identified. By comparing data with the known vibrational data of 1,2,3-trimethylbenzene and the results of ab initio calculations, we determined the electronic energies of the $D_1{\rightarrow}D_0$ transitions and vibrational mode frequencies in the ground electronic states of the 2,3-and 2,6-dimethylbenzyl radicals.

• Bulletin of the Korean Chemical Society
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• 제32권2호
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• pp.467-471
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• 2011

Spin exchange interactions of $(C_2N_2H_{10})[Fe(HPO_3)F_3]$ were examined by performing a spin dimer analysis based on extended Huckel tight binding method and a mapping analysis based on first principles density functional theory. Spin exchange interactions occur through the super-superexchange paths $J_1$ and $J_2$ in $(C_2N_2H_{10})[Fe(HPO_3)F_3]$. In the super-superexchange path $J_2$ magnetic orbital interactions between eg-block levels are much stronger than those from $t_{2g}$-block levels. Both electronic structure calculations show that the spin exchange interaction through the super-superexchange path $J_2$ is much stronger than that of $J_1$.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2565-2570
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• 2010

The orthorhombic $MgB_2C_2$ structure contains well-separated parallel graphite-like $B_2C_2^{2-}$ layers which extend infinitely in two dimensions. Three possible ways to distribute B and C atoms in the hexagonal sublattice sites are adopted. Band structures for the hypothetical distribution patterns are examined to assess the electronic stability of these phases and to account for the observed arrangement by means of extended Huckel tight-binding calculations. The preferred choice is the layer with B and C alternating strictly so that B is nearest neighbor to C and vice versa. A rationale for this is given. Due to the alternation of B and C within the honeycomb layers, $MgB_2C_2$ is a band insulator, which through partial substitution of Mg with Li, is predicted to turn metallic with holes in the $\sigma$ bands at the Fermi level.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3217-3220
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• 2010

The electronic structures and bonding configuration of histidine on Ge(100) have been investigated with various sample treatments using core-level photoemission spectroscopy (CLPES). Interpretation of the Ge 3d, C 1s, N 1s, and O 1s core level spectra being included in these systems revealed that both the imino nitrogen in the imidazole ring and the carboxyl group in the glycine moiety concurrently participate in the adsorption of histidine on a Ge(100) surface at 380 K. Moreover, we could clearly confirm that the imino nitrogen with a free lone pair in the imidazole group adsorbs on Ge(100) more strongly than the carboxyl group in the glycine moiety by examining systems annealed at various temperatures.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.610-616
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• 2014

The influence of solvent polarity on the absorption spectra of some synthesized azo dye with heterocyclic moieties and ${\beta}$-naphthol (1-3) have been investigated using a UV-Visible spectrophotometer. The spectral characteristics of the azo dyes (1-3) in different solvents at room temperature were analyzed. The solvatochromic empirical variables like ${\pi}^*$, ${\alpha}$, and ${\beta}$ have been used to discuss the solvatochromic behaviour of the dyes and to evaluate their contributions to the solute-solvent interactions. A multi-parameter regression model for quantitative assessment of the solute/solvent interaction and the absorption has been used to explain the solvent effect on azo dyes (1-3).

• Bulletin of the Korean Chemical Society
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• 제28권9호
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• pp.1485-1488
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• 2007

Photodissociation dynamics of cyanamide (NH2CN) at 212 nm has been investigated by measuring rotationally resolved laser induced fluorescence spectra of CN fragments exclusively produced in the ground electronic state. From the spectra, rotational population distributions of CN as well as translational energy releases in the products were obtained. The measured average rotational energies of CN were 12.4 ± 0.5 and 11.6 ± 0.5 kJ/ mol for v'' = 0 and v'' = 1, respectively and the center of mass average translational energy release among products was 41.8 ± 6.4 kJ/mol. The observed energy partitioning was well represented by statistical prior calculations, from which it was suggested that the dissociation takes place on the ground electronic surface after rapid internal conversion.

• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1062-1066
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• 2002

The complexes [Ni(L)(INT)2]${\cdot}$5H2O (1) and [Cu(L)(H2O)](Cl)(INT)${\cdot}$3H2O (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18 ,07.12 ]docosane, INT = isonicotinate) have been prepared and characterized by X-ray crystallography, electronic absorption, and cyclic voltammetry. The crystal structure of 1 reveals an axially elongated octahedral geometry with two axial isonicotinate ligands. The electronic spectra, magnetic moment, and redox potentials of 1 also show a high-spin octahedral geometry. However, 2 shows that the coordination environment around the copper atom is a distorted square-pyramid with an axial water molecule. The spectra and electrochemical behaviors of 2 are also discussed.

• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.981-985
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• 2003

Fluorine-19 NMR solution measurements have been made for various phenyl-fluorinated iron porphyrin complexes. Large chemical shifts for phenyl fluorine signals of iron(III) and iron(II) are observed, and these signals are sensitive to electronic structure. The chemical shift differences in ortho-phenyl fluorine signals between high-spin ferric and low-spin ferric tetrakis(pentafluorophenyl)porphyrins are approximately 40 ppm, whereas the differences are approximately 7 ppm between high- and low-spin states of ferrous tetrakis(pentafluorophenyl)porphyrin complexes. Analysis of fluorine-19 isotropic shifts for the iron(III) tetrakis(pentafluorophenyl) porphyrin using fluorine-19 NMR indicates there is a sizable contact contribution at the ortho-phenyl fluorine ring position. Large phenyl fluorine-19 NMR chemical shift values, which are sensitive to the oxidation and spin states, can be utilized for identification of the solution electronic structures of iron(III) and iron(II) porphyrin complexes.

• Bulletin of the Korean Chemical Society
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• 제31권4호
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• pp.850-858
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• 2010

The electronic absorption spectra of five Schiff bases derived from 2-hydroxy-1-naphthaldehyde with glycine, alanine, leucine, valine and phenylalanine have been measured in various solvents. The observed bands were assigned to the proper electronic transitions and compared with the predicted transitions at the semiempirical level of theory. The calculated equilibrium constants are in agreement with the experimental results, predicting the existence of all studied compounds predominantly or completely in keto-imine tautomerism. On the other hand, a correlation between $\nu\;(cm^{-1})$ (main frequency of each compound) and the well known solvent parameters $E_T$ (30), $\varepsilon_T$, $\pi^*$ been made. Furthermore, the acid dissociation constants, $pK_a$, were determined by using three different spectrophotometric methods.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2321-2324
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• 2013

An improved hybrid solar cell was obtained by focusing on the effects of ligand for CdSe nanoparticles, in the active layers. The performance was compared by mixing nanoparticles capped with pyridine or oleic acid for the acceptor material into poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester based active layer. The solar cells with pyridine capped CdSe nanoparticles showed a power conversion efficiency of 2.96% while oleic acid capped CdSe nanoparticles showed 2.85%, under AM 1.5G illumination. Formation of percolation pathways for carrier transport and a reduction in the hopping event resulted in better performance of pyridine capped nanoparticles.