• Journal of the Korean institute of surface engineering
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• v.56 no.6
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• pp.427-436
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• 2023

In the industry, it is recognized that human activities significantly lead to a large amount of wastewater, mainly due to the increased use of water and energy. As a result, the growing field of wastewater resource technology is getting more attention. The common technology for hydrogen production, water electrolysis, requires purified water, leading to the need for desalination and reprocessing. However, producing hydrogen directly from wastewater could be a more cost-effective option compared to traditional methods. To achieve this, a series of first-principle computational simulations were conducted to assess how waste nutrient ions affect standard electrolysis catalysts. This study focused on understanding the adsorption mechanisms of byproducts related to the oxygen evolution reaction (OER) in anion exchange membrane (AEM) electrolysis, using Co₃O₄ as a typical non-precious metal catalyst. At the same time, efforts were made to develop a comprehensive free energy prediction model for more accurate predictions of OER results.

• Journal of Photoscience
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• v.9 no.2
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• pp.51-54
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• 2002

We propose a novel mechanism (Twist Sharing Mechanism) for the cis-trans photoisomerization of rhodopsin, based on the molecular dynamics (MD) simulation study. New things devised in our simulations are (1) the adoption of Mt. Fuji potentials in the excited state for twisting of the three bonds C9=C10, C11=C12 and C13=14 which are modeled using the detailed ab initio quantum chemical calculations and (2) to use the rhodopsin structure which was resolved recently by the X-ray crystallographic study. As a result, we found the followings: Due to the intramolecular steric hindrance between 20-methyl and 10-H in the retinal chromophore, the C12-C13 and C10-C11 bonds are considerably twisted counterclockwise in rhodopsin, allowing only counterclockwise rotation of the C11 =C12 in the excited state. The movement of 19-methyl in rhodopsin is blocked by the surrounding three amino acids, Thr 118, Met 207 and Tyr 268, prohibiting the rotation of C9=C10. As a result only all-trans form of the chromophore is obtainable as a photoproduct. At the 90$^{\circ}$ twisting of C11=C12 in the course of photoisomerization, twisting energies of the other bonds amount to about 20 kcal/mol. If the transition state for the thermal isomerization is assumed to be similar to this structure, the activation energy for the thermal isomerization around C11=C12'in rhodopsin is elevated by about 20 kcal/mol and the thermal isomerization rate is decelerated by 10$\^$-14/ times than that of the retinal chromophore in solution, protecting photosignal from the thermal noise.

• Progress in Superconductivity
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• v.14 no.2
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• pp.99-101
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• 2012

Fluorescent yield X-ray absorption fine structure (XAFS) spectroscopy is useful for analyzing local structure of specific elements in matrices. We developed an XAFS apparatus with a 100-pixel superconducting tunnel junction (STJ) detector array with a high sensitivity and a high resolution for light-element dopants in wide-gap semiconductors. An STJ detector has a pixel size of $100{\mu}m$ square, and an asymmetric layer structure of Nb(300 nm)-Al(70 nm)/AlOx/Al(70 nm)-Nb(50 nm). The 100-pixel STJ array has an effective area of $1mm^2$. The XAFS apparatus with the STJ array detector was installed in BL-11A of High Energy Accelerator Research Organization, Photon Factory (KEK PF). Fluorescent X-ray spectrum for boron nitride showed that the average energy resolution of the 100-pixels is 12 eV in full width half maximum for the N-K line, and The C-K and N-K lines are separated without peak tail overlap. We analyzed the N dopant atoms implanted into 4H-SiC substrates at a dose of 300 ppm in a 200 nm-thick surface layer. From a comparison between measured X-ray Absorption Near Edge Structure (XANES) spectra and ab initio FEFF calculations, it has been revealed that the N atoms substitute for the C site of the SiC lattice.

• Journal of the Korean Chemical Society
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• v.55 no.5
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• pp.733-740
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• 2011

Multiple regression analysis was used for the calculation of pKa values of 15 substituted benzaldoximes by using various types of descriptors as parameters. These descriptors are based on quantum mechanical treatments. They were derived by employing semi-empirical calculation represented by the PM3 model and an Abinitio method expressed by Hartree-Fock(HF) model performed at the 6-311 G(d, p) level of theory. The parameters tested for their ability to represent the variations observed in the experimental pKa(s) are atomic and structural properties including Muliken charges on the atoms of hydroxyl group and C=N bond, the angle $C_6-C_1-C_7$, and length of O-H bond. Molecular properties are also used like energies of HOMO and LUMO, hardness(${\eta}$), chemical potential(${\mu}$), total energy(TE), dipole of molecule(DM), and electrophilicity index(W). The relation between pKa values and each of these parameters of the studied compounds is investigated. Depending on these relations, two sets of parameters were constructed for comparison between the PM3 and HF methods. The results obtained favor the Abinitio method for such applications although both models proved to have high predictive power and have sufficient reliability to describe the effect of substituents on pKa values of benzaldoxime compounds under consideration which is clear from the values of correlation coefficient $R^2$ obtained and the consistency between the experimental and the calculated values.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.405-411
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• 2011

The ab initio calculations for fluoromethyl fluoroperoxides have been carried out using MP2/6-311G(d,p) and B3LYP/6-311++G(d,p) method. The structural optimizations were performed for several isomers and conformers of methyl fluoroperoxide, $CH_3OOF$ and the vibrational frequencies were calculated. The most stable conformer of $CH_3OOF$ is skew form and has fairly short O-O bond distance. The trans and cis conformers have 8-12 kcal/mol higher energies than skew form and the other isomers are very unstable. The structures of $CH_2FOOF$, $CHF_2OOF$ and $CF_3OOF$ are also optimized and vibrational frequencies were calculated. These molecules also have skew forms as the lowest energy conformers. The O-O bond distances are longer and C-O bond distances are shorter than $CH_3OOF$, but the structural parameters are almost independent of the number of fluorine atoms in methyl group.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1422-1432
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• 2014

Convergent all-electron multi-reference configuration-interaction (MRCI) calculations are performed for a lithium dimer with Kaufmann's Rydberg basis functions. A comparison of the results of these calculations with those of the effective core potential/core polarization potential (ECP/CPP) method and experimental data reveals the deficiency of the all-electron ab initio method. The deficiency is related to the mere 51.9% attainment of electron correlation for the ground state. The percent attainment of electron correlation for the first excited state is slightly better than that for the ground state, preventing us from obtaining better agreements with experimental data by means of increasing the size of basis sets. The Kaufmann basis functions are then used with the ECP/CPP method to obtain the accurate convergent potential energy curves for the $^1\prod_u$ states correlated to Li(2p) + Li(2p) and Li(2s) + Li(n = 2, 3, 4). Quantum defect curves (QDCs) calculated for both the $X^2\sum_g$ and 1 $^2\prod_u$ states of the $Li{_2}^+$ ion and the Lu-Fano plot reveal a strong series-series interaction between the two $2snp{\pi}$ and $2pnp{\pi}$ Rydberg series. The QDCs are then used to resolve assignment problems in the literature. The reassignments, performed by Jedrzejewski-Szemek et al., of the dissociation product of the D $^1\prod$ state from (2s+3d) to (2s+3p) and that of the 6 $^1\prod_u$ from (2s+4d) to (2s+4p) are found to be incorrect. It may be more natural to assign their $2snp{\pi}$ Rydberg series as a $2snd{\pi}$ series. The state, assigned as 5p $^1\prod_u$ by Ross et al. and 4d $^1\prod$ by Jedrzejewski-Szemek et al., is assigned as the 7 $^1\prod_u$ state, correlated to the Li(2s) + Li(4f) limit.

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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• pp.1149-1156
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• 2008

The conformational study on neutral and zwitterionic L-alanines (N-Ala and Z-Ala, respectively) and the transition state (TS) for their interconversion is carried out using ab initio HF and density functional B3LYP methods with the self-consistent reaction field method in the gas phase and in solution. At both the HF and B3LYP levels of theory, the local minimum N1 for N-Ala is found to be most preferred in the gas phase and a weak asymmetric bifurcated hydrogen bond between the amino hydrogens and the carbonyl oxygen appears to play a role in stabilizing this conformation. The local minima N2a and N2b are found to be the second preferred conformations, which seem to be stabilized by a hydrogen bond between the amino nitrogen and the carboxylic hydrogen. The relative stability of the local minimum N2b is remarkably increased in solution than that in the gas phase. The local minimum N2b becomes more stable than the local minimum N2a in most of the solution. On the whole the relative free energies of Z-Ala and TS become more lowered, as the solvent polarity increases. N-Ala prevails over Z-Ala in aprotic solutions but Z-Ala is dominantly populated in ethanol and water. In aprotic solutions, the population of Z-Ala increases somewhat with the increase of solvent polarity. The barrier to Z-Ala-to-N-Ala interconversion increases on the whole with the increase of solvent polarity, which is caused by the increase of stability for Z-Ala.

• Journal of the Korean Ceramic Society
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• v.42 no.6 s.277
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• pp.391-398
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• 2005

It is known that $BaMgAl_{10}O_{17}:Eu^{2+}(BAM)$ phosphors currently used have a serious thermal degradation problem. We screened $SrO-B_2O_3-P_2O_5$ system by a solution combinatorial chemistry technique in an attempt to search for a thermally stable blue phosphor for PDPs. A Quantitative Structure Activity Relationship (QSAR) was also obtained using an artificial neural network trained by the result fiom the combinatorial screening. As a result, we proposed a promising composition range in the $SrO-B_2O_3-P_2O_5$ ternary library. These compositions crystallized into a single major phase, $Sr_6BP_5O_{20}:Eu^{2+}$. The structure of $Sr_6BP_5O_{20}:Eu^{2+}$ was clearly determined by ab initio calculation. The luminescent efficiency of $Sr_6BP_5O_{20}:Eu^{2+}$ was 2.8 times of BAM at Vacuum Ultra Violet (VUV) excitation. The thermal stability was also good but the CIE color chromaticity was slightly poor.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.215-220
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• 2002

The structures of 1-fluorosilatrane and the silatranyl cation were calculated by Hartree-Fock (HF), Mofller-Plesset second order (MP2), and various density functional theory (DFT) methods using many different basis sets, demonstrating that the Si-N bonds in two species are quite different. The N${\rightarrow}$Si bond distance of 1-fluorosilatrane from the hybrid DFT calculations $({\sim}2.32{\AA})$ using the Perdew-Wang correlation functional agrees with the gas phase experimental value $(2.324{\AA})$, while other functionals yield larger distances. The MP2 bond distance (2.287${\AA}$ with 6-311$G^{\ast}$) is shorter, and the HF one (2.544 ${\AA}$ with 6-311$G^{\ast}$) larger than those of DFT calculations. The MP2 bond distance is in good agreement with experiment indicating that the electron correlations are crucial for the correct description of the N${\rightarrow}$Si interaction. The silatranyl cation is a stable local minimum on the potential energy surface in all methods employed suggesting that the cation could be a reaction intermediate. The Si-N bond length for the cation is about 1.87 ${\AA}$ for all calculations tested implying that the Si-N bond is mainly conventional. Bonding characteristics of the Si-N bond in two species derived from the natural bond orbital analysis support the above argument based on calculated bond lengths.

• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1339-1343
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• 2005

The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.