• Bulletin of the Korean Chemical Society
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• v.22 no.9
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• pp.969-974
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• 2001

Model calculations for small molecules Li2, F2, LiF and BF have been performed at the Dirac-Fock level of theory using Dirac-Coulomb and Dirac-Coulomb-Magnetic Hamiltonians with various basis sets. In order to understand what may happen when the relativity becomes significant, the value of c, speed of light, is varied from the true value of 137.036 a.u. to 105 (nonrelativistic case) and also to 50 and 20 a.u. (exaggerated relativistic cases). Qualitative trends are discussed with special emphasis on the effect of the magnetic part of the Breit interaction term. The known relativistic effects on bonding such as the bond length contraction or expansion are demonstrated in this model study. Total energy, $\pi-orbital$ splitting, bond length, bond dissociation energy and dipole moment are calculated, and shown to be modified in a uniform direction by the effect of the magnetic term. Inclusion of the magnetic term raises the total energy, increases the bond length, reduces the $\pi-orbital$ splitting, increases the bond dissociation energy, and mitigates the changes in dipole moment caused by the Dirac term.

• Proceedings of the Materials Research Society of Korea Conference
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• 2007.11a
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• pp.83.1-83.1
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• 2007

• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1202-1204
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• 2014

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1682-1688
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• 2005

Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.23-28
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• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.510-514
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• 2011

Photodissociation dynamics of allyl alcohol ($H_2C$=CH-$CH_2OH$) has been investigated at 205 - 213 nm along the UV absorption band by measuring rotationally-resolved laser-induced fluorescence spectra of OH radicals. Observed energy partitioning of the available energy among products at all photon energies investigated was similar and the barrier energy for OH production is about 574.7 kJ/mol from the OH yield measurements. The potential energy surfaces for the $S_0$, $T_1$, and $S_1$ excited states along the dissociation coordinate were obtained by ab initio quantum chemical calculations. The observed energy partitioning was successfully modeled by the "barrier-impulsive model" with the reverse barrier and the geometry obtained by the calculated potential energy surfaces. The dissociation takes place on the $T_1$ excited state potential energy surface with an energy barrier in the exit channel and a large portion of the photon energy is distributed in the internal degrees of freedom of the polyatomic products.

• Journal of the Korean Society of Mineral and Energy Resources Engineers
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• v.55 no.6
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• pp.670-687
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• 2018

This paper reviews the structures, physical and chemical properties, origins and global distribution, amount of energy resources, production technologies, and environmental impacts of gas hydrates to understand the gas hydrates as future energy sources. Hydrate structures should be studied to clarify the fundamentals of natural gas hydrates, hydrate distributions, and amount of energy sources in hydrates. Phase equilibria, dissociation enthalpy, thermal conductivity, specific heat, thermal diffusivity, and fluid permeability of gas hydrate systems are important parameters for the the efficient recovery of natural gas from hydrate reservoirs. Depressurization, thermal stimulation, inhibitor injection, and chemical exchange methods can be considered as future technologies to recover the energy sources from natural gas hydrates, but so far depressurization is the only method to have been applied in test productions of both onshore and offshore hydrates. Finally, we discuss the hypotheses of environmental impacts of gas hydrates and their contribution to global warming due to hydrate dissociation.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.267-270
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• 2002

Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of $C_7H_7^+$ products were determined by examining their bimolecular reactivities toward toluene-$d_8$. The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of $C_7H_7^+$ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzyl cation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta >0.09 for ortho >0.05 for para.

• 한국지구물리탐사학회:학술대회논문집
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• 2003.11a
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• pp.695-702
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• 2003

In this study, an experimental apparatus has been designed and set-up to analyse the dissociating phenomena of hydrate in porous rock using electric heating method supplied at downhole. The electric heat injecting experiments have been performed to investigate the heat transfer within the core, the dissociating phenomena of hydrate, and the productivities of dissociated gas and water. These experiments were under constant heat injecting method as well as preheating methods. From the experimental results, it is seen that the hydrates is dissociated along the phase equilibrium curve and dissociation of hydrate is accelerated with heat. The injected heat is consumed for the dissociation and also it is lost together with outflow of the dissociated gas and water. From the investigation of gas producing behavior for various heat injecting methods, as the injected heat is greater, dissociation is accelerated faster at outlet and hence the initial gas production becomes higher. Also, it is shown that the initial gas productivity under the constant heating method is better, however, the energy efficiency is low because of smaller amount of the produced gas comparing to the amount of heat injected. In the experiments of preheating method, it was seen that gas production only initial stage is different with the preheating time, but the producing behaviors of gas production are similar.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.182-182
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• 2011

We investigated the adsorption structures of serine on a Ge(100) surface by core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. The core-level C 1s, N 1s, and O 1s CLPES spectra confirmed that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction, thereby favoring formation of the "O-H dissociated-N dative bonded" and "O-H dissociation bonded" structures at 0.30 ML and 0.60 ML, respectively. The experimental results were corroborated theoretically by calculating the reaction pathways leading to the two adsorption geometries. The reaction pathways indicated that the "O-H dissociated-N dative bonded structure" is the major product of serine adsorption on Ge(100) due to comparably stable adsorption energy.