• Bulletin of the Korean Chemical Society
• /
• 제31권7호
• /
• pp.1875-1880
• /
• 2010

A dicycle pyrazoline derivative, 1-phenyl-5-(p-fluorophenyl)-3,4-($\alpha$-p-fluoro-tolylenecyclohexano) pyrazoline, was synthesized and characterized by elemental analysis, IR, UV-vis, fluorescence spectra and X-ray single crystal diffraction. Density function theory (DFT) calculations were performed by using B3LYP method with 6-$311G^{**}$ basis set. The optimized geometry can well simulate the molecular structure. Vibrational frequencies were predicted, assigned and compared with the experimental values, which suggest that B3LYP/6-$311G^{**}$ method can well predict the IR spectra. Both the experimental electronic absorption spectra and the predicted ones by B3LYP/6-$311G^{**}$ method reveal three electron-transition bands, with the theoretical ones having some red shifts compared with the experimental data. Natural bond orbital analyses indicate that the absorption bands are mainly derived from the contribution of n $\rightarrow\pi^*$ and $\pi\rightarrow\pi^*$ transitions. Fluorescence spectra determination shows that the title compound can emit blue-light at about 478 nm. On the basis of vibrational analysis, the thermodynamic properties of title compound at different temperature have been calculated, revealing the correlations between $C^0_{p,m}$, $S^0_m$, $H^0_m$ and temperature.

• Journal of Astronomy and Space Sciences
• /
• 제15권2호
• /
• pp.335-340
• /
• 1998

IUE 저 분산 관측자료를 가지고 W-UMa 형 별인 44i Boo의 자외선 광도곡선을 완성하였다. 채층과 전이영역으로부터 나오는 방출선의 변화를 알아보기 위해서 CI, CII, CIV, SiIV, Hell 선의 방출선 세기를 계산하였다. CIV 방출 선이 가장 강한 방출을 보였으며, CII, Hell, CI, SiV의 순서로 방출선의 세기가 관측되었음이 확인되었다. 또한 방출선의 세기가 주기적으로 변하고 있음을 확인하였고, 모든 방출 선들이 위상 0.2와 0.8부근에서 상대적으로 강한 방출 선을 보인다. 이는 44i Boo의 표면에서 채층 및 전이영역의 활동성으로 인해 자외선 방출이 불 균일하게 나오고 있음을 나타내는 것이라고 해석할 수 있다. 채층 활동의 변화로 인해 관측시간이 서로 다를 때 자외선 방출선의 변광 형태도 달라지고 있음을 확인하였다.

• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 2001년도 하계학술대회 논문집
• /
• pp.713-716
• /
• 2001

In many papers, the electrochemical analysis of LiMn$_2$O$_4$shows the transition results of Mn$^{3+}$ ion. Charge ordering is accompanied by simultaneous orbital ordering due to the Jahn-Teller effect in Mnl$^{3+}$ ions. To analyze the cycle performance of LiMn$_{2-x}$Cu$_{x}$ O$_4$as the cathode of 4 V class lithium secondary batteries, XRD, TGA analysis were conducted. Although the cycle performance of the LiMn$_{2-x}$Cu$_{x}$ O$_4$was improved from pure LiMn$_2$O$_4$, the discharge capacity was significantly lower than LiCoO$_2$. In this paper, We study the Electrochemical characterization and enhanced stability of Cu-doped spinels in the LiMn$_{2-x}$Cu$_{x}$ O$_4$upon initial cycling.l cycling.

• 대한화학회지
• /
• 제19권4호
• /
• pp.218-224
• /
• 1975

바닥상태에 대한 자기무당착장 상호작용 에너지 이론을 2-치환-아크릴로니트릴과 시클로펜타디엔의 Diels-Alder 반응에 적용하여 반응성과 입체 선택성을 조사하였다. 출발점으로는 $\sigma$전자와 $\pi$전자를 다 고려하는 CNDO/2 MO가 사용되었다. 1차 상호작용 에너지 계산으로 정성적인 반응성이 얻어 졌으며 활성화 에너지 값은 실측치 범위의 것이 계산되었다. 2차 상호작용 에너지 계산으로 얻은 입체 선택성은 치환기에 대하여 모두 endo 선택성을 보여주었다. 비대칭 폐환의 원인을 반응원자의 원잣가 비활성 전자밀도로서 설명하였다.

• 대한화학회지
• /
• 제41권7호
• /
• pp.351-356
• /
• 1997

haloallene 유도체(1-halo-3-phenyl-1,2-propadiene)에 대해 EHMO계산을 하여, 에너지적으로 안정한 haloallene 분자의 구조를 결정하였다. MO 계산 데이터와 속도론적인 실험 결과로부터 haloallene의 가수분해반응 메카니즘을 제안하였다. pH 8.0 이하에서는 중간체로 carbonium ion Ⅱ이 생성되는 용매도움 $S_N1$ 메카니즘에 의해 진행된다. 그러나 pH 9.5 이상에서는 전위상태 Ⅲ를 거치는 $S_N2'$ 메카니즘에 의해 진행된다.

• Bulletin of the Korean Chemical Society
• /
• 제32권1호
• /
• pp.95-99
• /
• 2011

$CaTi_{1-x}Fe_xO_3(0{\leq}x{\leq}0.4)$ solid solution photocatalysts were synthesized by iron doping during the conventional solid state reaction at $1100^{\circ}C$ for 5 h and characterized by ultraviolet-visible (UV-vis) absorption spectroscopy, X-ray diffraction, morphological analysis. We found that $CaTi_{1-x}Fe_xO_3$ samples not only absorb UV but also the visible light photons. This is because the Fe substitution at Ti-site in $CaTi_{1-x}Fe_xO_3$ lattice induces the band transition from Fe3d to the Fe3d + Ti3d hybrid orbital. The photocatalytic activity of Fe doped $CaTiO_3$ samples for hydrogen production under UV light irradiation decreased with the increase in the Fe concentration. There exists an optimized concentration of iron in $CaTiO_3$, which yields a maximum photocatalytic activity under visible light ($\lambda\geq420nm$) photons.

• Bulletin of the Korean Chemical Society
• /
• 제11권1호
• /
• pp.25-28
• /
• 1990

The superconducting properties have been studied for high-Tc superconductors of the $Bi_{2-x}Mo_xSr_2Ca_2Cu_3O_y$ system (x = 0.03-0.30). The crystal structure is pseudo tetragonal with the average lattice parameters a = 5.38 ${\AA}$, b = 5.44 ${\AA}$ and c = 30.6 ${\AA}$. All samples exhibit superconductivity with Tc offset at 79 K and Tc onset at 90-115 K. The Tc onset point decreases with increasing x, but the Tc offset points are nearly the same for all samples. Scanning electron micrographs show a special growth behavior of the grains with a plate shape. It is suggested that the decrease in Tc onset points with substitution of Mo for Bi is due to the decrease in lattice parameters and to the p-orbital of Mo. It is concluded that Mo does not play a crucial role in the superconducting transition of the $Bi_2Sr_2Ca_2Cu_3O_y$ system.

• Bulletin of the Korean Chemical Society
• /
• 제11권1호
• /
• pp.49-54
• /
• 1990

The gas-phase thermolysis reactions of ${\alpha}$- and ${\beta}$-methylated ethyl formates, Y = $CH-X-CHR_1CH_2R_2$ where X = Y = O or S and $R_1\;=\;R_2$ = H or $CH_3$, are investigated theoretically using the AM1 method. The experimental reactivity order is reproduced correctly by AM1 in all cases. The thermolysis proceeds through a six-membered cyclic transition state conforming to a retro-ene reaction, which can be conveniently interpreted using the frontier orbital theory of three-species interactions. The methyl group substituted at $C_{\alpha}\;or\;C_{\beta}$ is shown to elevate the ${\pi}$-HOMO of the donor fragment (Y = C) and depress the ${\sigma}^{\ast}$-LUMO of the acceptor fragment ($C_{\beta}$-H), increasing the nucleophilicity of Y toward ${\beta}$-hydrogen which in turn increases the reactivity. The two bond breaking processes of the $C_{\alpha}$-X and $C_{\beta}$-H bonds are concerted but not synchronous so that the reaction takes place in two stages as Taylor suggested. The initial cleavage of $C_{\alpha}$-X is of little importance but the subsequent scission of $C_{\beta}$-H occurs in a rate determining stage.

• Bulletin of the Korean Chemical Society
• /
• 제19권7호
• /
• pp.733-737
• /
• 1998

Using an atom superposition and electron delocalization molecular orbital (ASED-MO) method, we have compared adsorption properties of adsorbates on the Pt(Ill) surface with the Pt(lll)/γ-Al203 surface in the ethylene hydrogenation reaction. In two-layer thick model systems, the calculated activation energy of the hydrogenation by the surface platinum hydride is equal to the energy by the hydride over supported platinum/γ-alumina. The transition structure on platinum is very close to the structure on the supported platinum/γ-alumina surface. Hydrogenation by the surface hydride on platinum can take place easily because the activation energy is about 0.5 eV less than hydrogenation by ethylidene. On supported platinum/,y-alumina the activation energy of the hydride mechanism is about 0.61 eV less than that of ethylidene mechanism. In one-layer thick model systems, the activation energy of hydrogenation by ethylidene is about 0.13 eV less than the activation energy of hydride reaction. The calculated activation energy by the hydride over the supported platinum y-alumina is 0. 24 eV higher than the platinum surface. We have found from this result that the catalytic properties of one-layer thick model systems have been influenced by the support but the two-layer thick model systems have not been influenced by the support.

• Bulletin of the Korean Chemical Society
• /
• 제27권9호
• /
• pp.1405-1417
• /
• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.