• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.367-375
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• 1992

The electronic structure change caused by insertion of hydrogen into the interstices of Pd cluster is studied. Several properties such as energy, reduced overlap population (ROP), electon density (ED) and density of states (DOS) are calculated by Extended Huckel Method. Various types of clusters are considered. The same is performed on Ni and Pt and all the results are compared. The results show that the hydrogen atom in Pd is stabilized remarkably but its wave function is almost unperturbed. The fact is compatible with noticeable solubility of hydrogen in Pd but may not be a positive enough evidence to rationalize the claimed cold fusion phenomenon. It is also found that a remarkable charge transfer from Pd atom to hydrogen atom occurs.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.385-388
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• 1992

The transition probabilities for the thermal intramolecular electron transfer and the optical intervalence transfer band for a symmetric mixed-valence Cu(I)-Cu(II) compound were used to extract the PKS parameters $\varepsilon$ = -1.15, ${\lambda}$ = 2.839, and ${\nu}g$- = 923 $cm^{-1}$. These parameters determine the potential energy surfaces and vibronic energy levels. Three pairs of vibrational levels are below the top of the energy barrier in the lower potential surface. The contribution of each vibrational state to the intramolecular electron transfer was calculated. It is shown that the three pairs of vibrational states below the top of the barrier are responsible for most of the electron transfer at 261-306 K. So the intramolecular electron transfer in this system is a tunneling process. The transition probability exhibits the usual high-temperature Arrhenius behavior, but at lower temperature falls off to a temperature-independent value as tunneling from the lowest levels becomes the limiting process.

• Bulletin of the Korean Chemical Society
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• v.10 no.5
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• pp.434-437
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• 1989

The pH dependence of the absorption and fluorescence of 4-hydroxy-2-methyl-1,2-benzothiazinenecarboxylat es, piroxicam and HMBDC have been measured and compared with the solvent dependence of the spectra reported previously. Four different prototropic species are observed in both ground and excited states of piroxicam ; the cation, the neutral, the anion and the dianion, while three different species such as the cation, the neutral and the anion are observed in HMBDC. The $pK_a$ and $pK_a^{\ast}$ have been determined by absorptiometric titration and Forster cycle method, respectively. The probable structure of each species has been proposed on the basis of the intramolecular phototautomerism.

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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• pp.458-461
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• 1986

The fluorescence intensity of khellin-dimethylfumarate C$_4$-cycloadduct (KDF) is very sensitive to temperature and to the nature of solvents, especially hydrogen-bonding ability. The fluorescence quantum yields of KDF in ethanol and isopentane at 77K are 0.73 and 0.54, respectively, both of which are much larger than the room temperature values. The phosphorescence lifetime is very long and decreases with decreasing the solvent polarity. The phosphorescence and fluorescence quantum yield ratio is very small and decreases with decreasing solvent polarity. The solvent relaxation plays an important role in the excited states of KDF. The internal conversion is a major decay process of the excited singlet state of KDF in all the solvents used at room temperature.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1065-1073
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• 1996

The dissociative recombination of O2+(v+)＋e-→O(1S)＋O(1D) has been theoretically investigated using the multichannel quantum defect theory (MQDT). Cross sections and rate coefficients at various electron energies are calculated. The resonant structures in cross section profile, which are hardly measurable in experiments, are also determined and the existence of Rydberg states is found to affect the rates. The theoretical rate coefficients are computed to be smaller than experimental ones. The reasons for this difference are explained. The two-step MQDT procedure is found to be very useful and promising in calculating the state-to-state rates of the dissociative recombination reaction which is a very important and frequently found phenomenon in Earth's ionosphere.

• Bulletin of the Korean Chemical Society
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• v.18 no.10
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• pp.1076-1082
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• 1997

The infrared, Raman, and jet-cooled laser-induced fluorescence excitation spectra of 1,2,3,4-tetrahydronaphthalene have been recorded and analyzed. The observed vibrations have been assigned to understand the conformational behaviors in its electronic ground (S0) and excited (S1) states. Ab initio at the HF/6-31G** level and molecular mechanics (MM3) force field calculations have been carried out to generate the complete normal mode frequencies of the molecule in its S0 state. The vibrational frequencies calculated from the ab initio method show a better agreement with the observed infrared and Raman frequencies than those calculated from the MM3 method. In several cases, the normal mode calculations were very helpful to clarify some ambiguities of previous assignments. In addition, the ring inversion process between two twisted conformers of 1,2,3,4-tetrahydronaphthalene has been reexamined utilizing ab initio calculation. The results show that the ring inversion energy is in the range of 3.7-4.3 kcal/mol which is higher than the previously reported AM1 value of 2.1 kcal/mol.

• Bulletin of the Korean Chemical Society
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• v.17 no.12
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• pp.1112-1117
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• 1996

The electronic structures of twenty-seven isomers of a macrocyclic fulleropyrrolidine are investigated with semi-empirical extended Huckel (EH) molecular orbital method. The geometry of each isomer is determined by the molecular mechanics and dynamics methods based on UFF (universal force field) empirical force field. The calculated geometries, such as the carbon-carbon distances of the fullerene moiety, are in good agreement with those of related fullerene derivatives. The EH calculation shows that the formation of macrocyclic pyrrolidine ring on fullerene moiety results in the reduction of the HOMO-LUMO energy gap. From the graphical analysis of the DOS (density of states), PDOS (projected DOS), and MOOP (molecular orbital overlap population) curves, we can find that this reduction is due to splitting of the HOMO of fullerene moiety, which results from the symmetry-breaking and the distortion of the buckminsterfullerene framework from its ideal icosahedral structure.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1441-1446
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• 1999

Laser-induced fluorescence (LIF) spectroscopy has been applied to study the supersonic jet of radicals of nitric oxide (NO) and atomic iodine produced in the flash pyrolysis of precursors n-butylnitrite (CH₃(CH₂)₃ONO) and allyl iodide (C₃$H_5$I), respectively. The systematic population analysis with spectral simulations demonstrates that the precursors are efficiently pyrolyzed and that radical beams show a substantial supersonic cooling. In addition, absence of local equilibrium was observed in the distributions of two electronic spin-orbit states ²Π$_{1/2}$ and ²Π$_{3/2}$ of NO products and can be rationalized in terms of the efficiency of collision-induced energy transfer rates.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.557-560
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• 1998

The structures and energies for the intramolecular rearrangement in $d^8-MCl(PH_3)_2$(HC≡CPh), M=Rh and Ir, complexes were studied by ab initio method at the Hartree-Fock and MP2 levels of theory. Three transition states in two pathways were optimized and characterized by frequency calculations. The activation energies for the process of π-type complex 1 to hydrido-alkynyl 2 have been computed to be relatively low 6.97 and 21.33 kcal/mol at MP2 level for Rh and Ir metals, respectively. However, the activation energies for a 1,2-hydrogen shift via t.s.3 have been computed to be high 50.83 and 60.05 kcal/mol for Rh and Ir metals.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.567-573
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• 1997

Photoinduced electron transfer from the charge-transfer excited states of Ru(tpy)(bpy(COOH)₂)$CN^+$, Ru(tpy)(bpy(COOH)₂)$Cl^+$, Ru(tpy)(bpy(COOH)₂)H₂+O², and Ru(tpy)(bqu(COOH)₂)$Cl^+$ to the conduction band of TiO₂ has been studied through photoelectrochemical methods. Ru(tpy)(bpy(COOH)₂)$CN^+$ produced the highest current density and open-circuit photovoltage, whereas Ru(tpy)(bqy(COOH)₂)$Cl^+$ produced the lowest values. A potential barrier was employed to explain the experimental result that the rate of the electron transfer increases with increasing the energy difference between the donor and acceptor. A sensitizer with a high current density yielded a high photovoltage and a high conversion efficiency. The reduction rate of the oxidized sensitizer decreased with the increases in the reduction potential of the sensitizer, resulting in a poor stability of a photoelectrochemical cell.