• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.610-611
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• 1989

• Journal of the Korean Chemical Society
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• v.5 no.1
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• pp.48-51
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• 1961

A calculation of the optical activity of the ${\alpha}$-1,2,3,4,5,6-Hexahalocyclohexane is presented based upon the Kirkwood's polarizability theory of optical rotatory power. The calculated specific rotation of the compound are given in the following table. The close agreements demonstrates the applicability of the polarizability theory to the compounds whose optical activity is due to steric interference. The agreement in sign also confirms the validity of the absolute configuration of the ${\alpha}$-1,2,3,4,5,6-Hexahalocyclohexane given by O. Hassel.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.860-864
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• 1994

2nd-order rate constants have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate (1), S-4-nitrophenyl thiobenzoate (2) and 4-nitrophenyl thionbenzoate (3) with alkoxides, aryloxides and thioaryloxides in absolute ethanol at 25.0 ${\pm}0.1$${\circ}C$. The substitution of O by polarizable S in the leaving group has little affected the reactivity of 2 toward the charge localized species (eg. $EtO^-$ and $CF_3CH_2O^-$), while the effect of the similar replacement in the carbonyl group has led to a decrease in reactivity by a factor of 10. However, the reactivity of these esters toward charge delocalized aryloxides has been found to be in the order $1<3{\le}2$. The effect of replaced sulfur atom on reactivity becomes more significant for the reaction with polarizable thioaryloxides, i.e. the reactivity increases in the order $1<2{\ll}3$. The difference in reactivity for the present system is attributed to a polarizability effect.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.632-636
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• 1992

Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

• Bulletin of the Korean Chemical Society
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• v.11 no.5
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• pp.362-364
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• 1990

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07a
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• pp.119-122
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• 2002

The calculated and measured dielectric constant of (1-x)(Al$\sub$1/2/Ta$\sub$1/2/)O$_2$-x(Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$(O$\leq$x$\leq$1.0) solid solutions were investigated by variations of ionic polarizability and crystal structure. (Al$\sub$1/2/Ta$\sub$1/2/)O$_2$ and (Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$were orthorhombic and tetragonal trirutile structure, respectively. When (Al$\sub$1/2/Ta$\sub$1/2/)O$_2$ was substituted by (Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$, the phase transformed to tetragonal structure over 60 mole%. Because the ionic radius of (Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$was slightly bigger than one of (A1$\sub$1/2/Ta$\sub$1/2)O$_2$, the cell parameters increased with an increase of (Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$ substitution. The measured dielectric constant increased with an increase of (Mg$\sub$1/3/Ta$\sub$2/3/)O$_2$ substitution and coincided with dielectric mixing rule and the calculated dielectric constant with the molecular additivity rule. There were some differences between the measured and the calculated dielectric constant. The reason of the lowered dielectric constant comparing with the calculated one was compressed stress due to the electronic structure of tantalum.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.201-206
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• 2013

The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. A linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${\o}$nsted-type plot, implying that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${\alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${\alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${\alpha}$-effect for the reaction of the more polarizable substrate 2.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2325-2329
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• 2013

Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.16 no.2
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• pp.108-112
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• 2003

The calculated and measured dielectric constants of (1-x)(A $l_{1}$2/ T $a_{1}$2/) $O_2$-x(M $g_{1}$3/ T $a_{2}$3/) $O_2$ (0$\leq$x$\leq$1.0) solid solutions were investigated by variations of ionic polarizability and crystal structure. (A $l_{1}$2/ T $a_{1}$2/) $O_2$ and (M $g_{1}$3/ T $a_{2}$3/) $O_2$ were orthorhombic and tetragonal trirutile structure, respectively. When (A $l_{1}$2/ T $a_{1}$2/) $O_2$ was substituted by (M $g_{1}$3/ T $a_{2}$3/) $O_2$, the phase transformed to tetragonal structure over 60 mole. Because the total ionic radius of [(Mg+2Ta)/3]$^{4+}$ was slightly bigger than one of [(Al+Ta)/2]$^{4+}$, the lattice parameters increased with an increase of (M $g_{1}$3/ T $a_{2}$3/) $O_2$ substitution. The measured dielectric constant increased with an increase of (M $g_{1}$3/ T $a_{2}$3/) $O_2$ substitution and coincided with dielectric mixing rule and the calculated dielectric constant with the molecular additivity rule. There were some differences between the measured and the calculated dielectric constant. The reason of the lowered dielectric constant comparing with the calculated one was compressed stress due to the electronic structure of tantalum.

• Korean Journal of Optics and Photonics
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• v.27 no.6
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• pp.223-228
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• 2016

The birefringence of distributed, uniaxially anisotropic molecules like liquid crystals is calculated as the degree of ordering is varied. The relation between the normalized birefringence ${\Delta}n_{rel}$ and the orientational order parameter S is investigated. The distribution function, which enables one to monitor the degree of ordering of liquid crystals including randomly distributed ones, is introduced. Using this distribution function, a series of distributed liquid crystals with order parameters ranging from 0 to 1 are generated, and ${\Delta}n_{rel}$ and S of the correspondingly distributed liquid crystals are calculated. Based on the calculated data, it is revealed that ${\Delta}n_{rel}$ and S satisfy the quasi-linear relation of $S=(1+a){\Delta}n_{rel}-a{\Delta}n^2_{rel}$, where a can be approximated as $n_o{\frac{{\Delta}n}{4}}$. The anisotropy of molecular polarizability is also calculated, using the birefringence, and separately following Vuks' method and Neugebauer's method, and it is shown that the relations between S and the molecular-polarizability anisotropy are also quasi-linear.