• 한국산학기술학회논문지
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• 제19권7호
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• pp.95-104
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• 2018

이성질체의 형태는 수용액 상태에서 종종 안정성과 반응성 등의 기본상태 뿐만 아니라 사슬성장 및 접힘 과정으로 인하여 형태형성에 영향을 주기 때문에 올리고펩티드의 형태를 이해하는 것이 중요하다. 본 논문에서는 L-알라닌(LA), 글리신(G) 5량체 모델의 무수 및 수화물(수화율; h/1) 상태의 구조와 에너지를 4가지 형태이성질체 (베타-확장형;= t-/t+, $PP_{II}$형; g-/t+, $PP_{II}$-유사형; g-/g+ 및 알파-나선형; g-/g-)에 대하여 B3LYP/6-31G(d,p)를 이용하여 양자화학계산(QCC) 방법으로 분석하였다. 구조최적화는 밀도함수 이론(DFT)으로써 B3LYP를 사용하였으며, 기본설정(Basic set)으로는 6-31G(d,p)를 이용하였다. 이미노 양성자(NH)를 갖는 LA와 G에서 베타-확장형, $PP_{II}$-유사형, 알파-나선형의 3가지 형태가 얻어졌으며, 대부분 물 분자가 $PP_{II}$-유사형과 알파-나선형에서는 CO-HN 분자 내 수소결합 사이에 주로 삽입되었고, 베타-확장형은 CO기에 부착되었다. 또한, LA와 G에서 $PP_{II}$-유사형 형태이성질체가 무수 및 수화물 상태에서 가장 안정적이었으며, $PP_{II}$ 형태이성질체는 얻어지지 않았다. LA에 대한 결과는 알라닌 올리고펩티드의 안정적인 형태가 주로 $PP_{II}$라고 보고한 다른 연구의 실험적 및 이론적인 결과와는 상이했다. 올리고펩티드 형태이성질체의 생성패턴과 안정성이 CO-HN의 분자 내 수소결합의 존재 여부 또는 출발 아미노산 내 $NH_2$기의 존재 여부에 강한 영향을 받는 것을 알 수 있었다.

• 대한화학회지
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• 제54권6호
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• pp.671-679
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• 2010

벤젠이온-물 복합체[$C_6H_6^+-(H_2O)_n$(n=1-5)]의 여러 가능한 구조를 예측하고 다양한 양자역학적 이론 수준(ab initio, DFT 등)에서 분자구조를 최적화 하였으며, 조화 진동주파수를 계산하여 IR 스펙트럼을 예측하였다. $C_6H_6^+-(H_2O)$에 대하여 보다 정확한 결합에너지를 구하기 위하여 MP2 수준에서 분자구조를 최적화하여 결합에너지 계산을 하여 B3LYP 계산 결과와 비교하였으며, 영점 진동에너지(zero-point vibrational energy)를 보정하여 실험값과 비교하였다. $C_6H_6^+-(H_2O)$에 대한 결합에너지는 MP2/aug-cc-pVTZ 이론수준에서 8.6 kcal/mol로 계산되어 최근의 실험결과($8.5{\pm}1$ kcal/mol)와 매우 잘 일치하는 것으로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1920-1926
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• 2008

We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2973-2978
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• 2009

The decomposition reaction mechanism of $CH_3CF_2O$ radical formed from hydroflurocarbon, $CH_3CHF_2$ (HFC-152a) in the atmosphere has been investigated using ab-initio quantum mechanical methods. The geometries of the reactant, products and transition states involved in the decomposition pathways have been optimized and characterized at DFT-B3LYP and MP2 levels of theories using 6-311++G(d,p) basis set. Calculations have been carried out to observe the effect of basis sets on the optimized geometries of species involved. Single point energy calculations have been performed at QCISD(T) and CCSD(T) level of theories. Out of the two prominent decomposition channels considered viz., C-C bond scission and F-elimination, C-C bond scission is found to be the dominant path involving a barrier height of 12.3 kcal/mol whereas the F-elimination path involves that of a 28.0 kcal/mol. Using transition-state theory, rate constant for the most dominant decomposition pathway viz., C-C bond scission is calculated at 298 K and found to be 1.3 ${\times}$ 10$^4s{-1}$. Transition states are searched on the potential energy surfaces involving both decomposition channels and each of the transition states are characterized. The existence of transition states on the corresponding potential energy surface are ascertained by performing Intrinsic Reaction Coordinate (IRC) calculation.

• Bulletin of the Korean Chemical Society
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• 제25권5호
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• pp.704-710
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• 2004

A poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) (PHDP) was prepared and its luminescence in tetrahydrofuran (THF) was studied. When PHDP is excited by UV light, it produces very strong blue luminescence. The quantum yield of PHDP (Q = 36.9%) is much greater than that of the monomer, 1-hexyl-3,4-dimethylpyrrole (HDP) with Q = 0.61%. The principal luminescence of PHDP has a single decay component with ca. 1 ns, whereas the decay of HDP is complicated. The molecular structure and conformational behavior of HDP and the oligomers up to trimer have been also determined by ab initio Hartree-Fock (HF/6-31$G^{**}$), density functional theory (DFT-B3LYP/6-31$G^{**}$), and semiempirical (ZINDO) methods. According to the results of calculations, it is proposed that the enhanced quantum yield of the polymer PHDP results mostly from the ${\pi}$-conjugation between neighboring pyrrole rings.

• Bulletin of the Korean Chemical Society
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• 제28권3호
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• pp.386-390
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• 2007

By use of a simple two-point extrapolation scheme estimating the correlation energies of the molecules along with the basis sets specifically targeted for extrapolation, we have shown that the MP2 basis set limit binding energies of large hydrogen-bonded complexes can be accurately predicted with relatively small amount of computational cost. The basis sets employed for computation and extrapolation consist of the smallest correlation consistent basis set cc-pVDZ and another basis set made of the cc-pVDZ set plus highest angular momentum polarization functions from the cc-pVTZ set, both of which were then augmented by diffuse functions centered on the heavy atoms except hydrogen in the complex. The correlation energy extrapolation formula takes the (X+1)-3 form with X corresponding to 2.0 for the cc-pVDZ set and 2.3 for the other basis set. The estimated MP2 basis set limit binding energies for water hexamer, hydrogen fluoride pentamer, alaninewater, phenol-water, and guanine-cytosine base pair complexes of nucleic acid by this method are 45.2(45.9), 36.1(37.5), 10.9(10.7), 7.1(6.9), and 27.6(27.7) kcal/mol, respectively, with the values in parentheses representing the reference basis set limit values. A comparison with the DFT results by B3LYP method clearly manifests the effectiveness and accuracy of this method in the study of large hydrogen-bonded complexes.

• Journal of Electrochemical Science and Technology
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• 제8권3호
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• pp.222-235
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• 2017

First, in this study, the inhibition efficiencies of metal complexes with Cu(II), Ni(II) and Zn(II) of STSC ligand for corrosion control of mild steel in oilfield formation water were investigated. The IEs for a mixture of 500 ppm STSC and 5 ppm metal ion ($Cu^{+2}$, $Ni^{+2}$, $Zn^{+2}$) were found to be 88.77, 87.96 and 85.13 %, respectively. The results were obtained from the electrochemical techniques such as open circuit potential, linear and tafel polarization methods. The polarization studies have showed that all used Schiff base metal complexes are anodic inhibitors. The protective film has been analyzed by FTIR technique. Also, to detect the presence of the iron-inhibitor complex, UV-Visible spectral analysis technique was used. The inhibitive effect was attributed to the formation of insoluble complex adsorbed on the mild steel surface and the adsorption process follows Langmuir adsorption isotherm. The surface morphology has been analyzed by SEM. Secondly, the computational studies of the ligand and its metal complexes were performed using DFT (B3LYP) method with the $6-311G^{{\ast}{\ast}}$ basis set. Finally, it is found that the experimental results were closely related to theoretical ones.

• EDISON SW 활용 경진대회 논문집
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• 제4회(2015년)
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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.

• Bulletin of the Korean Chemical Society
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• 제28권9호
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• pp.1539-1544
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• 2007

1-Phenyl-3-p-fluorophenyl-5-p-chlorophenyl-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-Vis and X-ray single crystal diffraction. Density functional calculations show that B3LYP/6-311G** method can reproduce the structural parameters. The electronic absorption spectra have been predicted based on the optimized structure by using 6-311G** and 6-311++G** basis sets and compared with the experimental values. The results indicate that TD-DFT method can only predict the electronic absorption spectra of the system studied here approximately. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between ,C0p,m,S0m,H0m and temperature.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2279-2285
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• 2011

The geometries, electronic structures and absorption spectra of the two organic triphenylamine-based dyes TA-St-CA and TA-DM-CA, containing identical electron donors and acceptors but the different conjugated bridges, were studied by density functional theory (DFT) at the B3LYP and PBE1PBE levels, respectively. The influence of para-orientating methoxyl units on the electronic structures and light absorption properties of the dyes and the consequent photovoltaic performance of the dye-sensitized solar cells (DSSCs) were investigated in detail. The results indicate that the introduction of the para-orientating methoxyl units into the conjugated bridge induces the increased absorption wavelength as well as the more negative EHOMO corresponding to the bigger driving force $(E_{I^-/I^-_3}-E_{HOMO})$ for dye reduction, which together improve the photovoltaic performance of TA-DM-CA, although there is a decline of the open circuit voltage caused by the more negative $E_{LUMO}$.