• Bulletin of the Korean Chemical Society
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• v.1 no.4
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• pp.117-121
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• 1980

The effect of lateral intermolecular interactions among the adsorbate molecules has been incorporated into the theory of multilayer physical adsorption developed previously by the present authors within the frame of Bragg-Williams approximation and the resulting adsorption isotherm has been used to interpret the adsorption data of tetramethylsilane vapor on clean iron film which we failed to account for in our previous works. The result has shown that up to the point where the relative pressure is about 0.7 considerable improvement is obtained but beyond this point there still remains large difference between theoretical and experimental isotherm. Such difference is supposed to arise from the neglect of effect of vertical interaction between the adsorbate molecules and the adsorbent surface.

• Bulletin of the Korean Chemical Society
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• v.4 no.2
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• pp.84-87
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• 1983

Transition state structures were calculated for A and M routes of ${\omega}$-alkenyl radical cyclization (n = 2∼4) using MINDO/3-RHF method. Results of our analysis of HOMO level changes indicated that the transition state stability is not controlled by the decoupling effect alone as Bischof suggested, but in greater degree it is determined by through-bond interaction of the HOMOs with the framework $HO-{\sigma}$ or $LU-{\sigma}^*$ orbitals. In case of larger n (n > 4), the product stability was considered to be the main cause of M route dominance in the cyclization.

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.369-374
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• 1994

Self-assembled (SA) and Langmuir-Blodgett (LB) monolayers of arachidic acid on silver surfaces have been investigated by a reflection-absorption Fourier transform infrared spectroscopy. Arachidic acid was adsorbed on silver as carboxylate with its two oxygen atoms bound symmetrically to the surface. Although both the SA and LB monolayers consisted of fully extended trans zigzag carbon chains, a closer examination indicated that the SA monotayers should possess a more ordered crystalline structure than the LB monolayers. The infrared spectral data dictated that the extent of methyl group exposure at the air-film interface was greater in the SA monolayers than the LB monolayers, in agreement with the contact angle measurement. From a theoretical analysis, the alkyl chains in each monolayers seemed to be tilted away from the surface normal by less than $3.5^{\circ}$, but in opposite directions. Arachidic acid monolayers were concluded to have same structure as stearic acid monolayers.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.565-570
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• 1992

The 1,5-sigmatropic rearrangements involving group (X) migration in ${\omega}$(X)-substituted 1,3-pentadiene, $C^1H_2=C^2H-C^3H=C^4H-C^5H_2-X$, where X = H, $CH_3$, $BH_2$, $NH_2$, OH or F, are investigated MO theoretically using the AM1 method. For the migrating groups without lone pair electrons, X = H, $CH_3$, or $BH_2$, the suprafacial pathway is favored, whereas for the migrating groups with lone pair electrons participating in the TS, $X=NH_2$, OH, or F, the antarafacial pathway is favored electronically. However excessive steric inhibition in the antarafacial TS for $X=NH_2$ leads to subjacent orbital controlled suprafacial process. The antarafacial shift of F is relatively disfavored compared to that of OH due to smaller orbital overlap and larger interfrontier energy gap in the TS.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.678-681
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• 1991

The Wittig-oxy-Cope rearrangements of deprotonated diallyl ether, I, $CH_2={\bar{C}}H-CH-O-CH_2-CH=CH_2$, have been investigated theoretically by the AM1 method. A two step mechanism forming a Wittig product ion, II, $(CH_2=CH)$ $(CH_2=CH-CH_2)$ $CHO^-$, through a radical-pair intermediate was found to provide the most favored reaction pathway in the Wittig rearrangement. The subsequent oxy-Cope rearrangement from species II also involves a two step mechanism through a biradicaloid intermediate. The intramolecular proton transfer in I (to form $CH_2=CH-CH_2-O-{\bar{C}}H-CH=CH_2$) is a higher activation energy barrier process compared to the Wittig and oxy-Cope rearrangements and is considered to be insignificant. These results are in good agreement with the condensed-phase as well as gas-phase experimental results.

• Bulletin of the Korean Chemical Society
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• v.15 no.3
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• pp.214-221
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• 1994

We present some results obtained from theoretical study on a non-symmetrical A/BC polymeric system including solvent which consists of two phases, a polymeric phase A on one side and a mixture of polymers B (as a compatibilizer) and C on the other in the presence of a solvent. By employing the functional integral techniques we derive the mean-field equations and solve them numerically to deduce the physical properties of the interface involving the polymers and solvent concentration profiles in the limit that molecular weights of all the polymers involved tend to infinity. The calculations are performed for typical values of the Flory interaction parameters and for the volume fraction of polymer B in the asymptotic phase and of solvent. In the polymers/solvent blend under consideration the interfacial adsorption of polymer B, the solvent concentration, and degrees of the specific interaction between the polymers are found to play important roles in modification of the interfacial properties.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.223-226
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• 1989

The chemical reactivity of 5,7-dimethoxycoumarine with adenosine has been calculated by the frontier electron and PPP-Cl MO methods. Results suggest that the major reactivity of the 5,7-dimethoxycoumarin is highest at the carbon-4 (position 4), whereas the electrophilic reactivity is generally spread all over the 5,7-dimethoxycoumarin molecule. These results are consistent with the experimental photoaddition reaction products. The small change of bond orders on excitation does not give enough reactivity to triplet states or the efficient intersystem crossing from $T_1\;to\;S_0$ inhibits photoaddition of 5,7-dimethoxycoumarine to adenosine. Although the relative intensity of the singlet band appears to be considerably higher than the triplet band intensity, its integrated intensity, i.e. oscillator strength, is comparable to that of the 5,7-dimethoxycoumarin and adenosine bands.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.227-230
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• 1989

The lowest excited state of styrylquinoxaline (StQx) has been studied by the SCF-MO-CI P-P-P and MM2 method. Results suggest that the lowest excited state is of a ${\pi},{\pi}^{\ast}(S_1$) nature with the n,${\pi}^{\ast}(S_2)$ state lying slightly above it. On the basis of these calculations the observed electronic spectra are discussed. The calculated absorption spectra are qualitatively similar to experimental ones with their characteristic visible bands. MM2 force field calculation suggested that the postulated conformers are different from each other in energy and planarity and are seperated by a barrier of about 4 Kcal/mole.

• Bulletin of the Korean Chemical Society
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• v.10 no.2
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• pp.161-167
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• 1989

The results of ab initio(MP2/6-31G) molecular orbital calculations of the dipole moment derivatives and gas phase IR intensities in chloromethanes are reported. The theoretical polar tensors are analyzed into the net charge, charge-flux, and overlap contributions. The charge-flux contribution was found to be dominant in the Cl atom polar tensor, while the net charge effect was the most prominent contribution for the H atom polar tensor. The Cl atom polar tensor appeared, in a good approximation, to be transferable among various chloro molecules. On the other hand, for the prediction of IR spectra of complex hydrocarbons containing chlorine atoms, some empirical adjustment of the H-atom polar tensor seemed to be made depending on the number of Cl atoms bound to the certain carbon atom.

• Analytical Science and Technology
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• v.34 no.1
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• pp.17-22
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• 2021

In this study, flame retardant mixtures of decabromodiphenylethane (DBDPE) and Sb2O3 were analyzed using Fourier transform infrared (FT-IR) spectroscopy. The experimentally obtained wavenumbers of DBDPE and Sb2O3 were 1321 and 949 cm-1, respectively, whereas those obtained by theoretical calculation were 1370 and 818 cm-1, respectively. Strong correlation was observed between the mixing molar ratios and observed peak area ratios, suggesting that FT-IR analysis can be used to obtain relative amounts of the individual components of flame retardant mixture.