• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.749-752
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• 2009

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.143-146
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• 2006

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1873-1876
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• 2006

• Bulletin of the Korean Chemical Society
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• v.3 no.2
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• pp.79-81
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• 1982

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2707-2710
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• 2012

The nucleophilic substitution reactions of O-ethyl phenyl phosphonochloridothioate with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE ($k_H/k_D$ = 0.93) to a primary normal DKIE ($k_H/k_D$ = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to frontside attack. A concerted $S_N2$ mechanism is proposed. A trigonal bipyramidal TS is proposed for a backside attack while a hydrogen-bonded, four-center-type TS is proposed for a frontside attack.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2797-2802
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• 2014

Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed for 8 based on the negative ${\rho}_{XY}$ (= -0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive ${\rho}_{XY}$ (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1829-1834
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• 2013

The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at $75.0^{\circ}C$. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ${\rho}_{XY}$ values, respectively. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.

• The Transactions of the Korean Institute of Electrical Engineers
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• v.33 no.5
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• pp.173-180
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• 1984

The spectra of scattering light fromlaser-produced plasma near its fundamental and second harmonic wavelength were observed respectively by means of spectroscopic technique. The experimental results and the generation mechanism of nonlinear effects such as the second garmonics and the brillouin scattering were analysed theoretically. The spectra of reflected laser light became wider than that of incident laser light. And the peak of spectrum of reflected light shifted to red-side from that of incident light. The second harmonic light is generated from the nonlinear interaction of the incident laser light and the electron plasma wave excited in resonance region by the oblique incidence of laser light to the plasma. The Brillouin backscattering from laser-produced plasmas of hydrogen and deuterium has shown an isotope effect in the red-side region of the generated second harmonic light. This isotope shift is explained by the parametric instability at the cutoff (resonance) region using frequency-and phase-matching conditions of the waves.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3811-3816
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• 2013

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

• Journal of Hydrogen and New Energy
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• v.14 no.4
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• pp.327-334
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• 2003

경수소와 중수소를 사용하여 Ti1.0Mn0.9V1.1합금의 경우 313K와 353 K에서, $Ti_{1.0}Cr1.5V_{1.1}$합금의 경우 313 K와 338K에서 각각 수소 동위체 효과를 조사하였다. 합금의 결정구조, 각 상의 존재량, 격자상수 등은 Rietveld method에 의해 결정되었다. 두 합금 모두 용도에 관계 없이 중수소의 흡장량이 경수소에 비하여 많았고, 이들 합금의 수소 동위체 효과는 LaNis 합금에 비하여 대단히 크게 나타났다. 실험 온도 범위에서 $Ti_{1.0}Mn_{0.9}V_{1.1}$합금의 경수소화물은 중수소화물에 비하여 안정하였고, Ti1.0Cr1.5V1.7합금에 있어서는 중수소화물이 더욱 안정하였다. 또한 $Ti_{1.0}Cr_{1.5}V_{1.7}$합금이 $Ti_{1.0}Mn_{0.9}V_{1.1}$합금보다 많은 량의 경수소와 중수소를 흡장하였다.