• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1227-1232
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• 2000

Near the conical intersection for the 1,2 $^{2}A'$ states of $H_3$ the derivative coupling vector is calculated and analyzed on the plane of internal coordinates, (U,V) or its polar coordinates $(S{\theta})$, based on the squares of the internuclear distances. It is shown that in the vicinity of the conical intersection the derivative coupling vector behaves like ${\theta}/2S$, which is responsible for the sign changes of the real-valued electronic wave function when the nuclear configuration traverses a closed path enclosing a conical intersection. The analytic property of the wave functions is studied and especially the observation of the sign change in the configuration state function (CSF) coefficients of the real-valued electronic wave functions is demonstrated.

• Bulletin of the Korean Chemical Society
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• 제22권12호
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• pp.1333-1336
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• 2001

A theoretical analysis is presented for the multichannel type resonance at energies above the dissociation threshold to O(1D) in the photodissociation of OH. Dissociations to both oxygenic terms O(3P) and O(1D) are treated. Total cross sections for producing these oxygen terms display asymmetric resonance due to the quantum interference resulting from complicated interplay of electronic states correlating to these two oxygenic terms. The branching ratios of O(3Pj, j = 0, 1, 2), and the vector properties of O(3Pj, j =0,1,2) and O(1D) display extensive changes near the threshold resonance as the result of the interactions among the electronic states correlated with O(3P) and O(1D).

• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1363-1368
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• 1998

Mo/γ-Al2O3 catalysts were prepared by impregnation method in various conditions to identify the states of surface Mo species. TPR (Temperature-Programmed Reduction) and Raman spectroscopy were applied to analyze the surface Mo species. TPR analysis revealed that MoO3 was reduced to Mo through MoO2, the intermediate state and the increase of Mo loading enhanced the reducibility of Mo oxide till the formation of monolayer coverage. High temperature calcination induced oxygen defects in MoO3 giving their unstable states for easier reduction. Raman spectroscopy analysis showed that the increase of Mo loading induced the polymeric Mo oxide.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.186-190
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• 1986

Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.225-234
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• 1993

As an application of the cluster orbitals proposed previously, nickel-, palladium-, and platinum-hydrogen systems are studied. Density of states, projected density of states, HOMO levels, and stabilization energies are calculated and compared with those obtained by extended Huckel method for small clusters. These calculations are extended to large clusters to find the size dependence of several physical quantities. Reduced overlap populations are also calculated to clarify the charge transfer phenomena reported earlier. The calculated physical quantities show no dependence on the cluster size. It is also found that the charge transfer occurs due to the intrinsic character of palladium, not due to the edge effect which may be present in small clusters.

• Bulletin of the Korean Chemical Society
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• 제15권3호
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• pp.228-236
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• 1994

The effect of the vibration mode coupling induced by the vibration-rotation interaction on total energy was investigated for the states with zero total angular momentum(J=0) in a quasilinear symmetric triatomic molecule of $AB_2$ type using a model potential function with a slight potential barrier to linearity. It is found that the coupling energy becomes larger for the levels of bend and asymmetric stretch modes and smaller for symmetric stretch mode as the excitation of the vibrational modes occurs. The results for the real molecule of $CH_2^+$, which is quasilinear, generally agree with the results for the model potential function in that common mode selective dependence of coupling energy is exhibited in both cases. The differences between the results for the model and real potential function in H-C-H system are analyzed and explained in terms of heavy mixing of the symmetric stretch and bend mode in excited vibrational states of the real molecule of $CH_2^+$. It is shown that the vibrational mode coupling in the potential energy function is primarily responsible for the broken nodal structure and chaotic behavior in highly excited levels of $CH_2^+$ for J= 0.

• Bulletin of the Korean Chemical Society
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• 제11권3호
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• pp.241-244
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• 1990

The photochemistry of 1-Methyl-2-cyclohexenyl aryl ketones (phenyl ketone 7a, p-toluyl ketone 7b, biphenyl ketone 7c and -naphthyl ketone 7d) is reported. The aryl ketone 7a, 7b and 7c undergo photo-racemization with efficiencies of 0.75, 0.79 and 0.76 respectively on direct irradiation. Direct irradiation of the ketone 7d, however, undergoes 1,3-shift with an efficiency of 0.02. Triplet states are responsible for the racemizations and singlet state is responsible for 1,3-shift as in general. The ketone 7a, 7b and 7c are good example of a few ${\beta},{\gamma}$-unsaturated ketones which undergo efficient intersystem crossing on direct irradiation.

• Bulletin of the Korean Chemical Society
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• 제19권3호
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• pp.308-313
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• 1998

A thermally irreversible photochromic system, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride (MTMA), has been studied by semi-empirical molecular orbital methods. There are one pair of stable conformations for the closed-ring form and three pairs for the open-ring form, each pair consisting of two mirror-image conformations. Interconversion between the parallel and anti-parallel conformations of the open-ring form is restricted due to high energy barriers. Only the anti-parallel conformation appears to be responsible for photochromic cyclization. Thermostability of the compound is attributed to an avoided crossing at high energy in the ground states of the isomers, whereas the photoreactivity can be explained by the mutually connected excited singlet (S1) states of the isomers, forming a double well potential with a low energy barrier. The large solvent effects can be partly explained with the low dipole moment of the anti-parallel conformation of MTMA in the S1 state. The large variation of quantum efficiency suggests that excess vibronic energy can be utilized to provide the activation energy for the photochromic reaction.

• Bulletin of the Korean Chemical Society
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• 제6권3호
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• pp.168-170
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• 1985

The pairing properties of electronic structure are investigated from ab initioists' point of view. Numerical results of exact ab initio effective valence shell Hamiltonian are compared with simple semiempirical Hamiltonian calculations. In the oxygen atom case it was found that effective three-electron interaction terms break the similarity between electron-states and hole-states. With the trans-butadiene as an example the pairing theorem was studied. Even for alternant hydrocarbons, the deviation from the pairing was found to be enormous. The pairing theorem, which is usually stated for semiempirical Hamiltonians, is not valid when the exact effective Hamiltonian is considered. The present study indicates that comparisons between the pairing theorem of semiempirical methods and ab initio effective Hamiltonian give important information on the accuracy of semiempirical methods.

• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.609-614
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• 2013

Extended H$\ddot{u}$ckel tight-binding band structure calculations are used to address the chemical bonding and elastic properties of $Zr_2AC$ (A=Al, Si, P, and S). Elastic properties are interpreted by analyzing the density of states and the crystal orbital overlap population for the respective phases. Our results show that the bulk modulus of these ternary compounds is determined by the strength of Zr-A bonds.