• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.674-678
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• 1991

Methanolysis of a ${\beta}$-lactam ring of a cephalosporin was simulated with AM1 semiempirical quantum mechanical calculation. The tetrahedral intermediate TD1 from an O-protonated cephalosporin and a methanol transfers the proton intramolecularly to the C-4 carboxylate to generate an oxyanion, i.e., second tetrahedral intermediate TD2, which undergoes the amide bond cleavage without further protonation on the N-5. For this cleavage a low-energy barrier TS2 was located. According to the energy diagram, tetrahedral intermediates easily undergo ring cleavage even without the protonation on the amide nitrogen.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.91-98
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• 2015

Formamide의 중성가수분해 mechanism은 QM/MM (quantum mecahnics/molecular mechanics) molecular dynamics simulations 및 CPMD과 같은 방법으로 연구되어왔다. 본 연구에서는. Umbrella sampling을 이용한 QM/MM-MD simulation을 사용하여 4가지 반응의 free energy surface를 도출해냈다. 전체적으로, 가장 선호되는 메커니즘은 two step으로 구성된 water assisted stepwise mechanism이었으며 모든 mechanism은 ab-initio calculation과 QM/MM-MD simulation이 수행되었다. water assisted stepwise mechanism을 살펴보면, 첫 번째 step에서 formamide의 carbonyl group이 hydrate되면서 gem-diol intermediate를 형성한다. 다음 step에서, intermediate의 hydroxyl group으로부터 amino group으로 water-assisted proton transfer이 일어난다. 두 반응 모두에서 물이 proton transfer를 직접적으로 도와주는 것을 관찰할 수 있었다. 특히, ab-initio calculation과는 다르게 QM/MM-MD에서는 gem-diol intermediate가 안정화되는 것으로 solvent effect를 잘 보여준다.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4098-4102
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• 2012

The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been explored using quantum chemical calculations. Possible reaction pathways to form five $C_3H_3N^{+{\bullet}}$ isomers have been obtained with Gaussian 4 model calculations. The rate constant for the HCN loss and the product branching ratio have been calculated using the Rice-Ramsperger-Kassel-Marcus theory on the basis of the obtained PES. The resultant rate constant agrees with the previous experimental result. By a kinetic analysis, it is proposed that the formation of $CH=CHC{\equiv}NH^{+{\bullet}}$ is favored near the dissociation threshold, while the formation of $CH=CHN{\equiv}CH^{+{\bullet}}$ is favored at high energies.

• Nuclear Engineering and Technology
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• v.56 no.6
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• pp.2079-2091
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• 2024

In this paper, a model is developed for calculating pH in the presence of organic impurities due to dissolution of paint and/or continuous injection of organic impurities in the sump. The model is implemented in the AnCheBi code for the analysis of chemical behaviors of the iodine in the containment when the pH changes during a severe accident. Validation of the model is performed with P10T2 and P11T1 experiments carried out by AECL in Canada under the BIP project. Importance analyses of the pH calculation model in the AnCheBi code are then performed with the aforementioned experimental data via Latin hypercube sampling on the reaction coefficients, sensitivity analyses of AnCheBi, and calculation of the correlation coefficients between the reaction coefficients and figure of merits (the pH and the concentrations of the various iodine species). From the importance analyses, we provide the sensitivity of the pH calculation model to the change of pH and the concentrations of the various iodine species and the reaction coefficients related with the dominant phenomena underlying the change of pH and the concentrations of the species.

• 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 Institute of Electronics Engineers of Korea SD
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• v.42 no.3 s.333
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• pp.9-16
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• 2005

The mobility in strained Si inversion layer on $Si_{1-x}Ge_x$ is calculated considering a quantum effect(subband energy and wavefunction) in inversion layer and relaxation time approximation. The quantum effect in inversion layer is obtained by using self-consistent calculation of $Schr\ddot{o}dinger$ and Poisson equations. For the relaxation time, intravalley and intervalley scatterings are considered. The result shows that the reason for the enhancement in mobility as Ge mole fraction increases is that the electron mobility in 2-폴드 valleys is about 3 times higher than that of 4-폴드 valleys and most electrons are located in 2-폴드 valleys as Ge mole fraction increases. Meanwhile, for the phonon-limited mobility the fitting to experimental data, Coulomb and surface roughness mobilities are included in total mobility, Deformation potentials are selected for the calculated effective field, temperature, and Ge mole fraction dependent mobilities to be fitted to experimental data, and then upgraded data can be obtained by considering nonparabolicity in Si band structure.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.229-240
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• 2002

Quantum mechanical calculation is performed for the $O(^1D)$ + HCl ${\rightarrow}$OH + Cl reaction using Reactive Infinite Order Sudden Approximation. Shifting approximation is also employed for the l ${\neq}$ 0 partial wave contributions. Various dynamical quantities are calculated and compared with available experimental results and quasiclassical trajectory results. Vibrational distributions agree well with experimental results i.e. product states mostly populated at $v_f$ = 3, 4. Our results also show small peak at $v_f$ = 0, which indicates bimodal vibrational distribution. The results show two significant broad peaks in ${\gamma}_i$ dependence of the cross section, one is at ${\gamma}_i$ = $15^{\circ}-35^{\circ}$ and the another is at ${\gamma}_i$= $55^{\circ}-75^{\circ}$ which can be explained as steric effects. At smaller gi, the distribution is peaked only at higher state ($v_f$ = 3, 4) while at the larger gi, both lower state ($v_f$ = 0) and higher state ($v_f$ = 3, 4) are significantly populated. Such two competing contributions (smaller and larger ${\gamma}_i$) result in the bimodal distribution. From these points we suggest two mechanisms underlying in current reaction system: one is that reaction occurs in a direct way, while the another is that reaction occurs in a indirect way.

• JSTS:Journal of Semiconductor Technology and Science
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• v.4 no.1
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• pp.63-73
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• 2004

A simple analytical model has been presented for the study of the optical bistability using a $GaAs-Al_{0.32}Ga_{0.68}As$ multiple quantum well (MQW) p-i-n diode structure. The calculation of the optical absorption is based on a semi-emperical model which is accurately valid for a range of wells between 5 and 20 nm and the electric field F< 200kV/cm . The electric field dependent analytical expression for the responsivity is presented. An attempt has been made to derive the analytical relationship between the incident optical power ( $(P_{in})$ ) and the voltage V across the device when the diode is reverse biased by a power supply in series with a load resistor. The relationship between $P_{in}$ and $P_{out}$ (i.e. transmitted optical power) is also presented. Numerical results are presented for a typical case of well size $L_Z=10.5nm,\;barrier\;size\;L_B=9.5nm$ optical wave length l = 851.7nm and electric field F? 100kV/cm. It has been shown that for the values of $P_{in}$ within certain range, the device changes its state in such a way that corresponding to every value of $P_{in}$ , two stable states and one unstable state of V as well as of $P_{out}$ are obtained which shows the optically controlled bistable nature of the device.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.67-76
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• 2009

The development of a variety of methods like AM1, PM3, PM5 and DFT now allows the calculation of atomic and molecular properties with high precision as well as the treatment of large molecules with predictive power. In this paper, these methods have been used to calculate a number of quantum chemical descriptors (like Klopman atomic softness in terms of $E_n^{\ddag}\;and\;E_m^{\ddag}$, chemical hardness, global softness, electronegativity, chemical potential, electrophilicity index, heat of formation, total energy etc.) for 75 alkanes to predict their boiling point values. The 3D modeling, geometry optimization and semiempirical & DFT calculations of all the alkanes have been made with the help of CAChe software. The calculated quantum chemical descriptors have been correlated with observed boiling point by using multiple linear regression (MLR) analysis. The predicted values of boiling point are very close to the observed values. The values of correlation coefficient ($r^2$) and cross validation coefficient ($r_{cv}^2$) also indicates the generated QSPR models are valuable and the comparison of all the methods indicate that the DFT method is most reliable while the addition of Klopman atomic softness $E_n^{\ddag}$ in DFT method improves the result and provides best correlation.

• Proceedings of the Optical Society of Korea Conference
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• 1995.06a
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• pp.127-137
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• 1995

Anomalously large real space charge transfer through thick barries in GaAs asymmetric double quantum wells is studied by photoluminesence exitation. This inter-well excitonic transfer is very large when the barrier is the Al0.3Ga0.7As alloy, but disappears when the barrier is GaAs/AlAs digital alloy with an equivalent Al concentration of 0.28. These resilts combined with observed x and barrier thickness depence suggest that the spatial fluctuation of the atomic arrangment of Ga and Al in the alloy may be responsible for this transfer. This picture is supported by the quantum mechanical calculation in three dimensions which takes into account the side fluctuation effects.