• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.3-15
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• 1992

Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, $(CO)_5Cr=CCHCH_2(XCH_3)\;,\;(CO)_5Mo=CCHCH_2(XCH_3)\;, and\;(CO)_5W=CCHCH_2(XCH_3)$, are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The ${\sigma}$ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the $(CO)_5M$. The ${\pi}$ bond is formed through the back-transfer of electrons from one of the degenerated d${\pi}$ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

• Aerospace Engineering and Technology
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• v.2 no.2
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• pp.151-156
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• 2003

Liquid rocket engine system is classified into an engine of pressurization and turbo pump type by the way of fuel fed-supporting system. In the KSR-III sounding rocket, an engine of pressurization type was used, but there was lots of technical problems to be solved for a use as the first stage engine of space launch vehicle. So, an engine of turbo pump type was required to be developed to overcome the technical limitation of liquid rocket engine. In this research, the analysis of propellant of Kerosine-LOX and methane-LOX which are noticed as a future propellant was carried out for the purpose of studying the basic characteristics. And to review the basic characteristics of an engine of turbo pump type, among the sizing variant of the space launch vehicle, the ways of injecting a satellite to a direct orbit and transient orbit were discussed in this paper.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.571-576
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• 1989

The relativistically parameterized Extended Huckel (REX) calculations are carried out for $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir). The calculated orbital and overlap populations agree with experimental data. The REX calculations on the electronic structure have been also compared with nonrelativistic EHT results. A ${\phi}$-bonding in M-Cl bond is founded to be more important for the $d^3$, $d^5$complexes than the $d^6$ system.

• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.85-94
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• 1973

The stability constants of the charge-transfer complexes formed between three derivatives of nitrobenzene, i.e., 1,3,5-trinitrobenzene, m-dinitrobenzene, nitrobenzene and eleven organic molecules such as $\alpha-picoline$, pyridine, dimethylsulfoxide, N, N'-dimethylacetamide, tetrahydrofurane, 1, 4-dioxane, diethyl ether, acetonitrile, propylene oxide, epichlorohydrine, and methyl acetate, have been determined by ultraviolet absorption spectroscopy in carbon tetrachloride solution at 25.0$^{\circ}C$. The parameters of the electrostatic effect ($E_D$) and covalent effect ($C_D$) for the eleven organic compounds have been calculated from the modified equation of the double-scale enthalpy,$logK = E_AC_A+E_DC_D$ and also the shift of C=O vibrational frequency in infrared spectra for N,N'-dimethylacetamide have been measured from the solutions of above organic compounds. The empirical equation, ${\Delta}{\nu}_{C=O} = 37.4-5.47E_D+12.1C_D$, related to the parameters and the frequency shift has been derived. It seems that the stabilities of the complexes principally depend on the covalent effect. Especially it is found that $\pi$ orbitals in molecules, in addition to the parameters, play the important role in forming the charge-transfer complexes.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.418-424
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• 1984

Rate constants for the hydrolysis of cinnamonitrile in the concentration range of 1 ∼ 5M of perchloric acid at 25$^{\circ}$C have been determined by UV spectrophotometry and from the Bunnett equations, hydration parameters (${\omega}$ = 9.8, ${\omega}^*$ = 0.42 & ${\phi}$=1.6) were obtained. CNDO/2 MO calculations were performed to determine relative stability, net charges, and overlap population of various conformational isomers. The results show that the (E)-planar is more stable than the (Z)-planar and protonation is favored on the nitrogen atom. On the basis of above findings, the acid hydrolysis is initiated by the protonation of the nitrogen atom of cinnamonitrile and then water molecule acting as nucleophile and as a proton transfer agent in the rate determining step. In the transition state of the acid hydrolysis, nucleophilic addition of water molecule occurs by sigma approach to the positively charged $C_7({\alpha}$) atom of the conjugate acid. As the results, we may conclude that the hydrolysis of cinnamonitrile in the strong acidic media proceeds through the A-2 type mechanism.

• The Journal of the Convergence on Culture Technology
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• v.7 no.2
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• pp.389-394
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• 2021

In this work, we study the properties of molecular structure and boundary orbital functions of the DPHMP-AlH and propiophenone and butyrophenone, which are forms of alkoxy-amine-aluminum derivatives. Furthermore, we investigate the effect on the selective reduction of the final products (R), (S)-phenylpropanol and (R), (S)-phenylbutanol by calculating the stereoscopic and thermodynamic parameters of the transition state. Considering the three-dimensional molecular structural stability, the transition status of (S) types DPHMP-AlH and alkylphenone was found to be more stable, resulting in the selective reductions of DPHM-AlH and alkylphenone from this result: (S)-(1)-phenylpropanol and (S)-(1)-phenylbutanol was confirmed that the formation was advantageous.

• Applied Biological Chemistry
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• v.26 no.2
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• pp.125-131
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• 1983

Formal net charges, bond populations, atomic orbital coefficients, energy components and conformation of dimethyl-2,2-dichlorovinylphosphate have been studied theoretically by using the CNDO/2 molecular orbital calculation method in attempt to describe the reactivity and the stability of the molecule. From the analysis of rate equation, molecular orbital calculations and identification of the hydrolysis products, 2,2-dichloroacetaldehyde and dimethylphosphoric acid, a mechanism of the hydrolysis of dimethyl-2,2-dichlorovinylphosphate(DDVP) has been proposed. The hydrolysis of DDVP proceeds through the mechanism of nucleophilic addition, typical Micheal reaction in basic media. Therefore, it appears probable that the attack by strong nucleophile, hydroxide ion occurs at the increased positive charge $C_2({\alpha})$ atom of a staggered conformation due to the inductive effect (-)I>(+)R of 2,2-dichlorovinyl, electron-attracting group. And then, the hydrolytic scission involves the $C_2({\alpha})-O_3$, ${\pi}-anti-bonding\;orbital({\pi}^*)$ in the subsequent reaction in aqueous solution.

• Journal of the Korean Chemical Society
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• v.31 no.2
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• pp.123-132
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• 1987

Nucleophilic substitution reactions of methylthiocyanate(MTC) with anion nucleophiles,$SH^-,\;CN^-$ and $OH^-$, have been investigated using MNDO method. For the three reaction centers of MTC, gas-phase and solution-phase selectivities are discussed for each nucleophile by considering potential energy profiles calculated(intrinsic term) and magnitudes of negative charge on the nucleophile at the transition state(solvation term). It was found that both components of the selectivity for $SH^-$agreed with the experimental results obtained for 4-methylbenzylthiocyanate (4-MBTC), but the selectivity order for TEX>$CN^-$ was found to agree only with that of the intrinsic term and that of $OH^-$disagreed with any theoretical selectivity order. The MNDO optimized geometries for all species at the stationary points are reported.

• Journal of the Korean Magnetics Society
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• v.17 no.5
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• pp.215-220
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• 2007

The superexchange interaction is introduced to explain antiferromagnetic ordering in transition metal compounds such as MnO and $MnF_2$. The anisotropic superexchange (Dzyaloshinskii-Moriya: DM) interaction can be derived by incorporating the spin-orbit interaction into the superexchange interaction. The anisotropic superexchange DM can account for the weak ferromagnetism observed in transition metal compounds such as ${\alpha}-Fe_2O_3$, $MnCO_3$, $CrF_3$.

• Korean Journal of Optics and Photonics
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• v.6 no.4
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• pp.352-358
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• 1995

Measurements of the Faraday rotation and magnetization of terbium-doped Hoya FR5 glass and cerium-doped Hoya FR4 glass have been made as a function of temperature T in the range 4.2 K -10 K and of magnetic field H of up to 80 kG at the $Ar^+$ laser wavelength of 514.5nm. The saturations of magnetization and Faraday rotation above H/T> $5kG.K^{-1}$ can be analyzed by the quantum theory of paramagnetism. Calculated parameters show that the large Verdet constant of $Ce^{3+}$ glass is due to the effective $4f\rightarrow5d$ electric dipole transition effect and that of $Tb^{3+}$ glass is due to the magnetization effect.effect.