• 제어로봇시스템학회:학술대회논문집
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• 1998.10a
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• pp.461-467
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• 1998

In spite of significant nonlinearities even in the simplest model, some types of steady-state and dynamic behavior common for nonlinear systems have never been associated with distillation columns. In recent years, multiplicity of steady states has been a subject of much research and is now widely accepted. Subsequently, stability of steady states has been explored. Another phenomenon that. although widely observed in chemical reactors, has not been associated with models of distillation columns is the existence of periodic oscillations. In this article we study the steady-state and dynamic behavior of the azeotropic distillation of the ternary homogeneous system methanol-methyl butyrate-toluene. Our simulations reveal nonlinear behavior not reported in earlier studies. Under certain conditions, the open-loop distillation system shows a sustained oscillation associated with branching to periodic solutions. The limit cycles are accompanied by traveling waves inside the column. Significant underdamped oscillations are also observed over a wide range of product rates.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2281-2285
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• 2013

The electronic structure, optical spectra, and thermodynamic properties of the three FOX-7 polymorphs (${\alpha}$, ${\beta}$, and ${\gamma}$) have been studied systematically using density functional theory. The LDA (CA-PZ) and generalized gradient approximation (GGA) (PW91) functions were used to relax the three FOX-7 phases without any constraint. Their density of states and partial density of states were calculated and analyzed. The band gaps for the three phases were calculated and the sequence of their sensitivity was presented. Their absorption coefficients were computed and compared. The thermodynamic functions including enthalpy (H), entropy (S), free energy (G), and heat capacity ($C_p$) for the three phases were evaluated.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.63-71
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• 1993

By use of cluster orbitals, analytic solutions of finite face-centered cubic clusters are obtained. Taking interactions between up to the second nearest neighbors into account, the forms of all the elements of the Hamiltonian matrix are found explicitly within Huckel approximation. By adopting $D_{2k}$ point group to the cluster, the matrix is simplified. We assume that the cluster orbitals can mix together only when their state indices are indentical. It is then possible to calculate various physical properties of face-centered cubic metal clusters and example are shown for palladium clusters. The results show that density of states and projected density of states are similar, qualitatively, with those obtained by extended Huckel calculation.

• Bulletin of the Korean Chemical Society
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• v.9 no.2
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• pp.101-105
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• 1988

The ab initio effective valence shell Hamiltonian method, based on quasidegenerate many-body perturbation theory, is generalized to calculate molecular properties as well as the valence state energies which have previously been determined for atoms and small molecules. The procedure requires the evaluation of effective operator for each molecular property. Effective operators are perturbatively expanded in powers of correlation and contain contributions from excitations outside of the multireference valence space. To demonstrate the validity of this method, calculations for dipole moments of several low lying valence states of OH, $OH^+$, and $OH^-$ to first order in the correlations have been performed and compared with configuration interaction calculations.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.13-18
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• 1982

The new substituent constants $({\sigma}^{\ast})$ are calculated from the acidity constants $(pK^{\ast})$ of phenol derivatives in the excited state ($^1L_b$). These substituent constant are applied to the Hammett equations and found good correlation with $pK^{\ast}$ of 2,6-di-tert-butyl phenol, benzamide, nitroaniline, thiophenol, azobenzene, and benzoic acid derivatives. The correlation was much better than that of ground state substituent constants such as ${\sigma},\;{\sigma}^+$, and ${\sigma}^-$. From these results, the new substituent constants $({\sigma}^{\ast})$are proposed to be used for the linear free energy relationship in the $^1({\pi},{\pi}^{\ast})$ excited states of phenyl compounds.

• Bulletin of the Korean Chemical Society
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• v.7 no.5
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• pp.391-395
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• 1986

MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.449-453
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• 1995

An exact quantum mechanical theory is employed to treat predissociation process of the $A^2{\Sigma}^+$ state of OH. The widths and positions of the lower (v= 2 and v= 3) rovibrational levels are calculated. Energy shifts of the resonances from the zeroth order (pure Hund'scase (b)) positions are shown to be small for N $\leq$ 10, indicating that the $A^2{\Sigma}^+$ state can be described as case (b) very well for low N. Due to the differential interactions of the $A^2{\Sigma}^+_{1/2}$ and $A^2{\Sigma}^+_{-1/2}$ states with $X^2II$and $2^2II$ states, small splittings between the $F_1$ and $F_2$ levels are predicted. Calculated lifetimes of the resonances agree with experimental results reasonably well.

• Bulletin of the Korean Chemical Society
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• v.17 no.5
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• pp.452-457
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• 1996

The effects caused by the ionization on the electronic structure and geometry on C60 are studied by the modified Su-Schriffer-Heeger (SSH) model Hamiltonian. After the ionization of C60, the bond structure of the singly charged C60 cation is deformed from Ih symmetry of the neutral C60 to D5d, C1, and C2, which is dependent upon the change of the electron-phonon coupling strength. The electronic structure of the C60+ cation ground state undergoes Jahn-Teller distortion in the weak electron-phonon coupling region, while self-localized states occur in the intermediate electron-phonon region, but delocalized electronic states appear again in the strong electron-phonon region. In the realistic strength of the electron-phonon coupling in C60, the bond structure of C60+ shows the layer structure of the bond distortion and a polaron-like state is formed.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.495-499
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• 1991

The changes in the free energy and hydration free energy of N-acetyl-N'-methylalaninamide in the unhydrated and hydrated states were calculated with ECEPP/2 and the hydration shell model. The configurational entropy change of each conformation in both states were computed by a harmonic method. To understand the hydration structure of each hydrated conformation, the hydration-shell coordination numbers of functional. groups of the molecule were estimated from water-accessible volumes, and the contributions of water-accessible volume and polarization of each group to the hydration free energy were analyzed. The results show a reasonable agreement with those of recent theoretical studies and experiments.

• Bulletin of the Korean Chemical Society
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• v.21 no.5
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• pp.497-502
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• 2000

Quantum mechanical analysis is presented for the photodissociation dynamics of the v'=4 levels of the $A^2Σ^+$ state of the OH molecule. We focus on the effects of the multichannel interactions between the asymptotically degenerate states in the recoupling region to see how they affect the dynamics near the predissociating resonances. Both the scalar (total cross section and branching ratios) and the vector properties (angular distributions and alignment parameters) of O($^3P_j, j=0, 1, 2) are treated. The resonances are predicted to be highly Lorentzian, and the branching ratios do not change much across them. Vector properties, however, show very delicate effects of the multichannel interactions and overlapping near the isolated and overlapping resonances. Computed resonance lifetimes agree reasonably well with experimental results.