• Korean journal of applied entomology
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• v.24 no.4 s.65
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• pp.231-238
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• 1986

Molecular orbital theoretical study on the stability of conformations and chemical reactivity of 0,0-diethylphenylphosphate derivatives were carried out by EHT and CNDO/2 molecular orbital calculation method. The results shown that the dipole moment(${\mu}$) and total energies of the ${\theta}=90^{\circ}$ conformer were ${\mu}=3.185D\;&\;E_t=-162.6479(au)$ and also that of the ${\theta}=0^{\circ}$ conformer were ${\mu}=5.596D\;&\;E_t=-162.4013(au)$, respectively. Therefore, the values of ${\mu}\;&\;E_t$ of the ${\theta}=90^{\circ}$ conformer were much smaller than that of the ${\theta}=0^{\circ}$ conformer. The form with angle of rotation ${\theta}=90^{\circ}$ of phenyl ring was shown to be most stable and this was interpreted in terms of electrostatic and steric effect. 0,0-diethylphenylphosphate derivatives are predicted to increase both charge and orbital controlled $SN_2$ reactivity of the electron withdrawing substituent reduces the HOMO & LUMO energy, while the electron withdrawing substituent due to increase in positive charge of phosphorus atom of phosphate molecule.

• Journal of Integrative Natural Science
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• v.3 no.4
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• pp.226-230
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• 2010

Calculation of partial charge is important in chemistry. However, because there are many methods developed, it is of considerable interest to know how to calculate and apply properly to address various chemical problems. For basis set, usually double zeta quality is acceptable, and double zeta polarization function would be enough for most cases. To describe electronic state more accurately, Many electron configurations would be necessary to describe highly strained or anionic species. The NPA population introduced new concept about amide bonds, i.e., the planar geometry of nitrogen atom may not come from resonance, but from the lowering of p-orbital energy by electronegative carbonyl carbon atom. The issues for hypervalent atomic charges was also addressed by various charge derivation scheme. When the charge schemes were applied to organolithium compounds, the ionic nature of boding was revealed. This comes from the fact that previous Mulliken partial atomic charges overemphasized the covalent character, wihout much justification. The other partial charge derivation schemes such as NPA(natural population analysis), IPP (Integrated Projected Population) showed that much more ionic picture. ESP potential derived charges are generally believed to be suitable to describe intermolecular interactions, therefore they are used for molecular dynamics simulations and CoMFA (comparative molecular field analysis). The charge derivation schemes using multipole polarization was mainly applied to reproduce experimental infrared spectroscopy. In some reports these schemes are also suitable for intermecular electrostatic interactions. Charges derived from electron density gradient have shown the some bonds are not straight, but actually bent. The proper choice of charge-calculation method along with suitable level of theory and basis set are briefly discussed.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.40-47
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• 2015

본 연구에서는 일치환된 방향족 화합물의 $NO_2{^+}$ 치환반응에서의 반응성 (reactivity)과 지향성 (regioselectivity)에 대해 분석하였다. 기존의 연구에 따르면, 방향족 고리와 치환체 사이의 ${\sigma}$ 결합을 통한 유발효과와 ${\pi}$ 결합을 통한 공명효과로 인해 벤젠 고리의 전자 분포가 증가하게 되면 반응성이 증가하는 것으로 알려져 있다. 또한 반응중간생성물인 탄소양이온의 안정성을 통해 지향성을 확인할 수 있는 것으로 알려진 바가 있다. 이에 따라, 본 연구에서는 반응성과 지향성이 실험적으로 잘 알려진 7가지의 치환기 (OH, $OCH_3$, $CH_3$, Cl, COOH, CN, $NO_2$)를 선정하여 DFT functional인 B3LYP를 사용하여 natural bond orbital (NBO) 계산을 하였고, 각각의 일치환된 벤젠 고리가 갖는 전자 분포를 ${\sigma}$와 ${\pi}$ 전자로 나누어서 보기로 했다. 그 결과, 일치환된 방향족 고리 치환반응의 반응성과 지향성은 ${\sigma}$ 결합을 통한 유발효과에 의해서는 영향을 받지 않고, 공명 효과로 인한 반응물의 ${\pi}$ 전자 분포에 의해 결정되는 것을 확인할 수 있었다. 이외에도 반응성을 비교 하기 위해 친핵체로 작용하는 일치환된 방향족 고리의 highest occupied molecular orbital(HOMO) 에너지와 친전자체인 $NO_2{^+}$의 lowest unoccupied molecular orbital (LUMO) 에너지의 차이를 비교하였으며, 친핵체의 HOMO 에너지가 높을수록 반응성이 커짐을 알 수 있었다.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.1-4
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• 1970

The methyl group does not possess an unshared pair of electrons. But F.A. Matsen has introduced the concept of the methyl group as a Pseudo-heteroatom which contributes a pair of electrons to ${\pi}$ system. In this heteroatom model, A. Streitwieser et al have assumed that the electrons in a methyl group behave to their approximation as a single electron pair on a single atom. But the theoretical basis on the heteroatom model hyper-conjugation has not studied yet. In this paper, Linear combination of Bond orbital and group theory is used to investigate the theoretical basis for it.

• Textile Coloration and Finishing
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• v.27 no.4
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• pp.270-274
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• 2015

Molecules always show broad absorption band envelopes, and this results from the vibrational properties of bonds. The width of an absorption band can have an important influence on the color of a dye. A narrow band imparts a bright, spectrally pure color to the dye, whereas a broad band can give the same hue, but with a much duller appearance. Typically, half-band widths of cyanine dyes are about 25nm compared to value of over 50nm for typical merocyanine dyes. Thus, cyanine dyes are exceptionally bright. The factors influencing the width of an absorption band can be understood with reference to the Morse curves. The width of the absorption band depends on how closely the bond order of the molecules in the first excited state resembles that in the ground state. We have quantitatively evaluated the "molecular structure-absorption band shape" relationship of dye molecules by means of Pariser-Parr-Pople Molecular Orbital Method(PPP-MO).

• Current Optics and Photonics
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• v.1 no.4
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• pp.402-411
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• 2017

Combined LIBS-Raman spectroscopy has been widely studied, due to its complementary capabilities as an elemental analyzer that can acquire signals of atoms, ions, and molecules. In this study, the classification of polymorphs was performed by laser-induced breakdown spectroscopy (LIBS) to overcome the limitation in molecular analysis; the results were verified by Raman spectroscopy. LIBS signals of the $CaCO_3$ polymorphs calcite and aragonite, and $CaSO_4{\cdot}2H_2O$ (gypsum) and $CaSO_4$ (anhydrite), were acquired using a Nd:YAG laser (532 nm, 6 ns). While the molecular study was performed using Raman spectroscopy, LIBS could also provide sufficient key data for classifying samples containing different molecular densities and structures, using the peculiar signal ratio of $5s{\rightarrow}4p$ for the orbital transition of two polymorphs that contain Ca. The basic principle was analyzed by electronic motion in plasma and electronic transition in atoms or ions. The key factors for the classification of polymorphs were the different electron quantities in the unit-cell volume of each sample, and the selection rule in electric-dipole transitions. The present work has extended the capabilities of LIBS in molecular analysis, as well as in atomic and ionic analysis.

• Journal of Korean Society of Environmental Engineers
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• v.36 no.6
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• pp.442-450
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• 2014

Concern has grown over a presence of micropollutants in natural water since sulfonamide antibiotic substances such as sulfamethazine, sulfamethoxazole, sulfathiazole have been frequently detected in Nakdong River, Korea. The current work investigates the degradation of the three sulfonamide substances by using quantum chemistry calculations of density functional theory (DFT) and experimental measurement techniques of Fourier transform infrared spectroscopy (FT-IR) and ultraviolet-visible spectrophotometer (UV-VIS). DFT calculations demonstrate that the lowest energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbitals (LUMO) lies in sulfanilamide functional group of sulfonamide, implying that the sulfanilamide functional group would be the most active site for ozone oxidation. Also, UV-VIS spectra and FT-IR analysis reveal that 260 nm band originated from sulfanilamide group was absent after ozone oxidation, indicating that a functional group of amine (N-H) was removed from sulfanilamide. Both theoretical and experimental observations agree well with each other, demonstrating the DFT calculation tool can be an alternative tool for the prediction of chemical reactions in purification treatment processes.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.142.2-142.2
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• 2016

The metal intercalation to an organic semiconductor is of importance since the charge transfer between a metal and an organic semiconductor can induce the highly enhanced conductivity for achieving efficient organic electronic devices. In this regard, the changes of the electronic structure of copper phthalocyanine (CuPc) caused by the intercalation of potassium are studied by ultraviolet photoemission spectroscopy (UPS) and density functional theory (DFT) calculations. Potassium intercalation leads to the appearance of an intercalation-induced peak between the highest molecular occupied orbital (HOMO) and the lowest molecular unoccupied orbital (LUMO) in the valence-band spectra obtained using UPS. The DFT calculations show that the new gap state is attributed to filling the LUMO+1, unlike a common belief of filling the LUMO. However, the LUMO+1 is not conductive because the ${\pi}$-conjugated macrocyclic isoindole rings on the molecule do not make a contribution to the LUMO+1. This is the origin of a metal-insulator transition through heavily potassium doped CuPc.

• Proceedings of the KIEE Conference
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• 2008.05a
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• pp.181-182
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• 2008

고 효율의 유기 발광 소자 개발을 위해 무엇보다 발광 소자의 각층의 에너지 대 구조를 고려한 구조 개선과 새로운 유기물질 합성을 통해 구동전압을 낮춤으로써 전력효율을 높이고, 소모 전력을 낮추며, 수명을 증가시킬 수 있어, 많은 연구자들이 유기 발광 소자의 효율을 향상시키기 위해 다양한 노력들을 시도하고 있다. 본 연구에서는 고 효율화를 위한 방법으로 유기 발광 소자에 있어서 전자주입에 필요한 전압을 낮추고 전자 주입을 촉진시키기 위하여 발광물질의 LUMO(LOWEST UNOCCUPIED MOLECULAR ORBITAL) 준위와 음극 금속의 페르미 준위를 고려하여 전자 주입시 전위 장벽을 낮출 수 있는 에너지 대 구조를 가진 전자 주입 층을 검토하였고, 정공 주입을 촉진시키기 위하여 양극 금속의 페르미 에너지 준위와 발광 층의 HOMO(HIGHEST OCCUPIED MOLECULAR ORBITAL) 준위를 고려하여 정공 주입시 전위장벽을 낮출 수 있는 적절한 에너지 대 구조를 가진 정공 주입 층에 대하여 고찰하였다.

• Journal of the Korean Applied Science and Technology
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• v.27 no.1
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• pp.1-5
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• 2010

HOMO(the highest occupied molecular orbital) and LUMO(the lowest unoccupied molecular orbital) of four recalcitrant polycyclic aromatic hydrocarbons (PAHs) were calculated by MOPAC program(CaChe Co). The previous papers which reported experimental results about radical reaction of PAHs were reviewed. The reported radical reaction positions of four PAHs corresponded with predicted positions in which ${\Delta}E$(HOMO-LUMO) was high. From these results, it appears that determining the ${\Delta}E$(HOMO-LUMO) of a PAH is a promising method for predicting the radical reaction position.