• Bulletin of the Korean Chemical Society
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• v.24 no.6
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• pp.763-770
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• 2003

The $BH_5$ molecule, which is suggested as an intermediate of the acidolysis of $BH_4^-$, contains a weak two-electron-three-center bond and it requires extremely high-level of theories to calculate the energy and structure correctly. The structures and energies of $BH_5$ and the transition state for the hydrogen scrambling have been studied using recently developed multi-coefficient correlated quantum mechanical methods (MCCMs). The dissociation energies and the barrier heights agree very well with the previous results at the CCSD(T)/ TZ(3d1f1g, 2p1d) level. We have also calculated the potential energy curves for the dissociation of $BH_5$ to $BH_3$ and $H_2$. The lower levels of theory were unable to plot correct potential curves, whereas the MCCM methods give very good potential energy curves and requires much less computing resources than the CCSD(T)/ TZ(3d1f1g,2p1d) level. The potential energy of the $BH_5$ scrambling has been obtained by the multiconfiguration molecular mechanics algorithm (MCMM), and the rates are calculated using the variational transition state theory including multidimensional tunneling approximation. The rate constant at 300 K is 2.1 × $10^9s^{-1}$, and tunneling is very important.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2008.04a
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• pp.259-264
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• 2008

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2007.11a
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• pp.306-313
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• 2007

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3873-3879
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• 2011

The potential energy surface (PES) for the isomerizations and dissociations of the acrylonitrile radical cation was determined from the CBS-QB3 and CBS-APNO calculations. The Rice-Ramsperger-Kassel-Marcus model calculations were performed based on the PES in order to predict the competitions among the dissociation channels. The mechanisms for the loss of $H^{\bullet}$, $H_2$, $CN^{\bullet}$, HCN, and HNC were proposed. The $C_3H_2N^+$ ion formed by loss of $H^{\bullet}$ was predicted as a mixture of $CH{\equiv}C-C=NH^+$, $CH{\equiv}C-N{\equiv}CH^+$, and $CH_2=C-C{\equiv}N^+$. Furthermore $CH{\equiv}C-C{\equiv}N^{+{\bullet}}$ was formed mainly by a consecutive 1,2-H shift and 1,2-H2 elimination.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.136-142
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• 1990

PMO (Pertubation Molecular Orbital) energies, ${\delta}E$, have been calculated from NBMO (Nonbonding Molecular Orbital) coefficient for some hydrocarbons by PMO method. It was found that the stabilization energies are correlated with activation energies, bond dissociation energies, and G-values observed from vapor phase radiolysis in the free radical reactions.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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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.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.652-658
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• 1991

The effect of intermolecular collisions in the infrared multiphoton dissociation (IRMPD) of difluorochloromethane was investigated using He, Ar, and $N_2$ as buffer gases. The reaction probability for IRMPD of difluorochloromethane was measured as a function of laser fluence and the buffer gas pressure under unfocused beam geometry. It was observed that the reaction probability was initially enhanced with the increase of buffer gas pressure up to about 20 torr, but showed a decline at higher pressures. The reaction probability increases monotonically with the laser fluence, but the rate of increase diminishes at higher fluences. An attempt was made to simulate the experimental results by the method of energy grained master equation (EGME). From the parameters that fit the experimental data, the average energy loss per collision, $<{\Delta}E>_d$, was estimated for the He, Ar, and $N_2$ buffer gases.

• Journal of the Semiconductor & Display Technology
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• v.7 no.3
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• pp.35-39
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• 2008

We study the interaction of acetone molecule $[(CH_3)_2CO]$ on Si(001) surface using density functional theory. An acetone molecule is adsorbed on a Si atom of the Si dimer of the Si(001) surface. The adsorption of the acetone molecule on the Si atom at lower height between the two Si atoms of the dimer is more favorable than that on the Si atoms at upper height. Then we calculate an energy variation of dissociation and four-membered ring structures of the acetone molecule adsorbed on the Si surface. Total energy difference between the two structures is about 0.05 eV, indicating that the two structures are almost equally stable. Energy barrier exists when a hydrogen atom is dissociated and adsorbed on the other Si atom of the dimer, while energy barrier does not exist when the adsorbed acetone molecule changes to four-membered ring structure, except for the rotation of the acetone molecule along z-direction. Therefore, four-membered ring structure is kinetically more favorable than the dissociation structure when the acetone molecule is adsorbed on the Si(001) surface.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.2
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• pp.206-212
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• 2011

The effect of process parameters on $H_2$ production from water vapor excited by HF ICP has been qualitatively examined for the first time. With the increase of ICP power, characteristics of $H_2$ production from $H_2O$ dissociation in plasma was divided into 3 regions according to both reaction mechanism and energy efficiency. At the edge of region (II) in the range of middle ICP power, energy effective hydrogen production from $H_2O$ plasma can be achieved. Furthermore, within the region (II) power condition, heating of substrate up to $500^{\circ}C$ shows additional increase of 70~80% in $H_2$ production compared to $H_2O$ plasma without substrate heating. This study have shown that combination of optimal plasma power (region II) and wall heating (around $500^{\circ}C$) is one of effective ways for $H_2$ production from $H_2O$.

• Journal of the Korean Solar Energy Society
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• v.30 no.1
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• pp.34-41
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• 2010

Gas hydrates are solid solutions when water molecules are linked through hydrogen bonding and create host lattice cavities that can enclose many kinds of guest(gas) molecules. There are plenty of methane(gas) hydrate in the earth and distributed widely at offshore and permafrost. Several schemes, to produce methane hydrates, have been studied. In this study, depressurization method has been utilized for the numerical model due to it's simplicity and effectiveness. IMPES method has been used for numerical analysis to get the saturation and velocity profile of each phase and pressure profile, velocity of dissociation front progress and the quantity of produced gas. The values calculated for the sample length of 10m, show that methane hydrates has been dissolved completely in approximately 223 minutes and the velocity of dissociation front progress is 3.95㎝ per minute. The volume ratio of the produced gas in the porous media is found to be about 50%. Analysing the saturation profile and the velocity profile from the numerical results, the permeability of each phase in porous media is considered to be the most important factor in the two phase flow propagation. Consequently, permeability strongly influences the productivity of gas in porous media for methane hydrates.