• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.191-191
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• 2012

InP quantum dot (QD) - organosilicon nanocomposites were synthesized and their photoluminescence quenching was mainly investigated because of their applicability to white LEDs (light emitting diodes). The as-synthesized InP QDs which were capped with myristic acid (MA) were incompatible with typical silicone encapsulants. Post ligand exchange the MA with a new ligand, 3-aminopropyldimethylsilane (APDMS), resulted in soluble InP QDs bearing Si-H groups on their surface (InP-APDMS) which allow embedding the QDs into vinyl-functionalized silicones through direct chemical bonding, overcoming the phase separation problem. However, the ligand exchange from MA to APDMS caused a significant decrease in the photoluminescent efficiency which is interpreted by ligand induced surface corrosion relying on theoretical calculations. The InP-APDMS QDs were cross-linked by 1,4-divinyltetramethylsilylethane (DVMSE) molecules via hydrosilylation reaction. As the InP-organosilicon nanocomposite grew, its UV-vis absorbance was increased and at the same time, the PL spectrum was red-shifted and, very interestingly, the PL was quenched gradually. Three PL quenching mechanisms are regarded as strong candidates for the PL quenching of the QD nano-composites, namely the scattering effect, Forster resonance energy transfer (FRET) and cross-linker tension preventing the QD's surface relaxation.

• 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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• 제32권12호
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• pp.4210-4214
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• 2011

Quasiclassical trajectory (QCT) calculations of Ne + ${H_2}^+$ reaction have been carried out on the adiabatic potential energy surface of the ground state $1^2$ A'. The reaction probability of the title reaction for J = 0 has been calculated, and the QCT result is consistent with the previous quantum mechanical wave packet result. Quasiclassical trajectory calculations of the four polarization-dependent differential cross sections have been carried out in the center of mass (CM) frame. The P(${\theta}_r$), P(${\phi}_r$) and P(${\theta}_r$, ${\phi}_r$) distributions, the k-k'-j' correlation and the angular distribution of product rotational vectors are presented in the form of polar plots. Due to the well in $1^2$ A' PES, the reagent vibrational excitation has greater influence on the polarization of the product rotational angular momentum vectors j' than the collision energy.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.531-538
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• 2014

The quantum mechanical properties of a series of oligo-para-phenylenes (2-11) were characterized using DFT B3LYP/6-311G(d,p) calculations. The global minimum among the various torsional conformers of an oligo-p-phenylene is calculated to be a twist conformation. A less stable planar conformation, in which all the dihedral angles in oligo-p-phenylene are restricted to be planar, has also been calculated. The total electronic energies, normal vibrational modes, Gibbs free energies, and HOMOs and LUMOs of the two different conformations (twisted and planar) of the oligo-p-phenylenes were analyzed. The energy differences between the HOMOs and LUMOs of the substrates are in accord with the maximum absorption peaks of the experimental UV spectra of 2-6. The calculated normal vibrational modes of 2-6 were comparable with their experimental IR spectra.

• Bulletin of the Korean Chemical Society
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• 제6권2호
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• pp.103-107
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• 1985

Quantum chemical calculations were carried out to explain how the electronic states of some series compounds vary with metabolic activation. Compounds studied included aromatic amines and amides, polycyclic hydrocarbons, and a few alkylating agents that do not require metabolic activation. The 1, 2 and 4 positions forming the trans-butadiene frame of a molecule, henceforth referred to as "the trans 1, 2, 4 region", have seen to be important positions for the prediction of carcinogenic activity of these compounds. It is also evident that their electrophilic properties increase with metabolic activation. That is the sum of ${\pi}$-electron densities of the trans 1, 2, 4 region in the lowest unoccupied molecular orbital (LUMO) has been found to increase in the order of precarcinogens < proximate-ones < the carbocation ultimate-ones. This is consistent with the fact that chemical carcinogens become more strongly electrophilic with activating. This region not only provides a unified view of structurally diverse carcinogens, but also predicts uniformity in their reactive sites. Accordingly, we suggest that an understanding of the trans 1, 2, 4 region would be helpful in elucidating the mechanism of carcinogenesis.

• 한국산학기술학회논문지
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• 제16권2호
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• pp.1563-1570
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• 2015

본 연구는 올리고펩티드의 연쇄성장 과정에서의 배좌의 변화를 조사하기 위하여 알라닌 올리고머 모델의 2량체 부터 5량체 까지 양자화학 계산(QCC)에 의한 구조최적화 계산을 하였다. 말단기의 영향을 확인하기 위하여 N말단 및 C말단이 공히 amide 구조를 갖는 "amide type" ($CH_3CONH-and-CONHCH_3$)과 N말단만이 methyl 구조를 갖는 "methyl type" ($CH_3NH-and-CONHCH_3$)의 2종류 모델을 준비하였다. 5량체 까지의 구조 최적화 계산 결과 3종류의 형태이성질체로 수렴이 되었다. 안정성이 높은 순서로 각각 ${\alpha}$ 나선형, PPII 유사형, ${\beta}$ 확장형으로 나타났으며, 사슬회전 방향이 서로 반대인 형태이성질체간의 에너지 값은 동일하게 나타났다 (5량체, "amide type" 좌 우회전형: ${\Delta}E=-1.05$, "methyl type" 좌 우회전형: ${\Delta}E=-1.62$). ${\alpha}$ 나선형의 모노머 단위당 에너지변화(${\Delta}E$)는 모노머의 증가와 함께 감소하였다.

• 공업화학
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• 제8권2호
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• pp.262-266
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• 1997

실리카 표면 수산기를 나타내는 분자모델에 대해 CNDO/2계산을 수행하여 Wiberg결합차수, 전체에너지, LUMO에너지, 쌍극자모멘트 및 형식전하를 얻었다. 제안된 모델들의 Br${\ddot{o}}$nsted산성도는 Wiberg결합차수를 이용하여 서술하였다. 계산된 결합차수값들은 수소결합에 따라 큰 차이를 나타내었다. 그러나 실리카 표면수산기의 Lewis산성도는 수산기의 구조와 무관하였다.

• Corrosion Science and Technology
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• 제21권1호
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• pp.21-31
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• 2022

Potentiodynamic polarization, EIS measurements, quantum chemical calculations, and molecular dynamic simulations were used to investigate the corrosion behavior of mild steel in 0.5 M aqueous hydrochloric acid medium in the presence or absence of nystatin drug. Potentiodynamic tests suggested that this molecule could act as a mixed inhibitor due to its adsorption on the mild steel surface. The objective of this study was to exploit theoretical calculations to gain a better understanding mechanism of inhibition. Calculating the adsorption behavior of the investigated molecule on Fe (1 1 0) surface was accomplished using Monte Carlo simulation. Molecules were also investigated using Density Functional Theory (DFT), specifically PBE functional, in order to identify the link between molecular structure and corrosion inhibition behavior of the compound under investigation. Adsorption energies between nystatin and iron were estimated more accurately by utilizing Molecular Mechanics calculation with Periodic Boundary Conditions (PBC). Estimated theoretical parameters significantly assisted our understanding of the corrosion inhibition mechanism exhibited by this molecule. They were found to be in accord with experimental results.

• 공업화학
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• 제7권2호
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• pp.321-325
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• 1996

$Cu^{n+}$ 교환된 Y형 제올라이트 상에서 진행되는 NO분해반응의 특성을 양자화학적 계산을 통해 해석하였다. 제올라이트내 양이온 자리를 나타내는 Cluster모델들에 대해 CNDO/2와 같은 이론적 계산을 수행하여 전체에너지, LUMO에너지 및 Wiberg결합차수값들을 얻었다. 각 모델들의 전체에너지와 결합차수값들을 통해 제올라이트 골격내 $Cu^{n+}$ 양이온 자리에서의 NO분해반응에 대한 반응기구를 고찰하였다. 제안된 분자모델들은 각기 다른 Si/Al비와 $Cu^+$ 및 $Cu^{2+}$ 교환된 양이온의 경우로 구분하여 고찰하였다. LUMO에너지의 계산을 통해 모델분자들의 L산성도를 해석하였다. NO분해반응의 메카니즘은 NO의 흡착, $N_2$ 및 $O_2$로의 분해, $N_2$ 및 $O_2$의 탈착의 단계가 연속적으로 진행될 가능성이 있었다. 양이온 자리에서 $Cu^{2+}$는 $Cu^+$ 보다 더 강한 L산성을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.