• 제목/요약/키워드: Jahn-Teller

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$La_{0.7}Ca_{0.3-x}Ba_xMnO_3$ manganites : Local structure and transport properties

  • A.N.Ulyanov;Yang, Dong-Seok;Yu, Seong-Cho
    • Proceedings of the Korea Crystallographic Association Conference
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    • 2003.05a
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    • pp.8-8
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    • 2003
  • Electron-phonon interaction plays a significant role in forming of colossal magnetoresistance effect (CMR). Polaron formation was observed by neutron diffraction and by extended X-ray absorption fine structure (EXAFS) analysis. Local probe as given by the EXAFS is a useful method to study the polaronic charge and its dependence on temperature and ions size. Here we present the EXAFS study of polaronic charge in La/sub 0.7/Ca/sub 0.3-X/Ba/sub X/MnO₃ compositions. The single phase La/sub 0.7/Ca/sub 0.3-X/Ba/sub X/MnO₃ manganites (x=0; 0.03; 0.06, ..., 0.3) were prepared by ceramic technology [1]. The Curie temperature was determined by extrapolation of the temperature dependence of the magnetization (down to zero magnetization). EXAFS experiments were carried out at the 7C EC beam line of the Pohang Light Source (PLS) in Korea. The atomic pair distribution functions (PDF) were obtained by re-regularization method [2] from filtered spectra. The PDF for the x=0.3 sample showed a single peak function and for x=0.0, 0.03, 0.06, 0.09, 0.12 compositions were asymmetric in agreement with a small Jahn-Teller elongation of two (short and long) bonds of the MnO/sub 6/ octahedron. Dispersion, σ/sub Min-O//sup 2/, and asymmetry, σ/sub Min-O//sup 3/, of the Mn-O bond distances varied significantly with x and showed a maximums at x=0.09. The maximum of σ/sub Min-O//sup 2/ is caused by increase of dynamic rms displacements of the Mn-O distances near the T/sub C/. The observed x dependence of σ/sub Min-O//sup 3/ reflects the reduction of charge carriers mobility at approaching to T/sub C/ from low as well as high temperatures.

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Synthesis, Structure and Magnetic Properties of Mn12 Single Molecule Magnet Containing 4-(Methylthio)benzoate as Peripheral Ligands

  • Lim, Jin-Mook;Do, Young-Kyu;Kim, Jin-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1065-1070
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    • 2005
  • $[Mn_{12}O_{12}(O_2CPh-4-SMe)_{16}(H_2O)_4]{\cdot}7CH_2Cl_2$ (1), a new single-molecule magnet complex has been successfully synthesized by substitution of acetate ligand of Mn12ac with 4-(methylthio)benzoic acid. Complex 1 crystallizes into triclinic P$\overline{1}$ with a = 18.321(3) $\AA$, b = 19.011(3) $\AA$, c = 27.230(4) $\AA$, $\alpha$ = 86.973(3)$^{\circ}$, $\beta$ = 76.919(3)$^{\circ}$, $\gamma$ = 87.613(3)$^{\circ}$, and Z = 2. In complex 1, one Mn(III) ion has an abnormal Jahn-Teller elongation axis oriented at an oxide ion. Complex 1 has two out-of-phase ac susceptibility peaks in the 2-4 K and 4-7 K regions. Effective anisotropy energy barrier and pre-exponential factor are $U_{eff}$ = 45.95 K, 1/$\tau$0 = 8.6 ${\times}\;10^9s^{-1}\;for\;{\chi}_M$'' peaks in the lower temperature region and $U_{eff}$ = 59.45 K, 1/$\tau_0$ = 2.2 ${\times}\;10^8\;s^{-1}$ for $\chi_M$'' peaks in the higher temperature region. The parameters of S = 10, g = 1.87, D = -0.40 $cm^{-1}$, and E = 0.00034 $cm^{-1}$ were obtained from the M/N${\mu}_B$ vs. H/T plot of complex 1.

Charge-discharge Properties by Cut-off Voltage Changes of Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$ and ${LiMn_2}{O_4}$in Li-ion Secondary Batteries (코발트와 니켈로 치환한 리튬이온 이차전지 Cathode, Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$${LiMn_2}{O_4}$의 Cut-off 전압 변화에 따른 충방전 특성)

  • 유광수;박재홍;이승원;조병원
    • Journal of the Korean Ceramic Society
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    • v.38 no.5
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    • pp.424-430
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    • 2001
  • Cut-off 전압 변화에 따른 충방전 특성을 알아보기 위하여 Mn을 다른 전이 금속이 Co와 Ni로 소량 치환시킨 Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$(M=Ni, Co, $\delta$=0, 0.05, 0.1, 0.2)를 고상 반응법으로 80$0^{\circ}C$에서 48시간 동안 유지하여 합성하였다. 충방전의 cut-off 전압은 2.5~4.4V, 3.0~4.5V, 3.5~4.5V, 3.5V~4.7V의 네 가지 전압범위고 하였다. 충방전 실험결과, Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$의 용량은 각각 Co와 Ni의 $\delta$=0.1에서 최대를 보였다. Co 치환 조성 재료와 순물질 모두에서 최대의 용량을 보인 cut-off 전압대는 3.5~4.5V 이었는데 이때의 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$와 LiM $n_2$ $O_4$의 초기 충전용량과 초기 방전용량은 각각 118, 119mAh/g과 114, 104mAh/g 이었다. 또한 모든 cut-off 전압대에서 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$는 순수한 LiM $n_2$ $O_4$보다 더 높은 용량과 우수한 싸이클 성능을 보였으며 그 결과는 밀착형 전지구성에서도 일치하였다.하였다.

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Structural and electrochemical characterization of K2NiF4 type layered perovskite as cathode for SOFCs (K2NiF4 type 층상 페롭스카이트 구조 La(Ca)2Ni(Cu)O4-δ의 SOFC 양극 특성 및 결정구조 평가)

  • Myung, Jae-ha;Hong, Youn-Woo;Lee, Mi Jai;Jeon, Dae-Woo;Lee, Young-Jin;Hwang, Jonghee;Shin, Tae Ho;Paik, Jong Hoo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.25 no.3
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    • pp.116-120
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    • 2015
  • $La_2NiO_{4+{\delta}}$ based oxides, a mixed electronic-ionic conductors (MIECs) with $K_2NiF_4$ type structure, have been considerably investigated in recent decades as electrode materials for advanced solid oxide fuel cells (SOFCs) due to their high electrical conductivity, and oxidation reduction reaction (ORR). In this study, structure properties of $La(Ca)_2Ni(Cu)O_{4+{\delta}}$ were studied as a potential cathode for intermediate temperature SOFCs (IT-SOFCs).

Investigation of Electronic Structures of TCr2O4 (T = Fe, Co, Ni) Spinel Oxides by Employing Soft X ray Synchrotron Radiation Spectroscopy (연 X선 방사광 분광법을 이용한 TCr2O4(T = Fe, Co, Ni) 스피넬 산화물의 전자구조 연구)

  • Kim, Hyun Woo;Hwang, Jihoon;Kim, D.H.;Lee, Eunsook;Kang, J.S.
    • Journal of the Korean Magnetics Society
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    • v.23 no.5
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    • pp.149-153
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    • 2013
  • The electronic structures of $TCr_2O_4$ (T = Fe, Co, Ni) spinel oxides have been investigated by employing synchrotron radiation-based soft X ray absorption spectroscopy (XAS). The measured 2p XAS spectra of transition-metal ions reveal that Cr ions are trivalent ($Cr^{3+}$), and all the T (T = Fe, Co, Ni) ions are divalent ($Fe^{2+}$, $Co^{2+}$, $Ni^{2+}$). It is also found that most of T (T = Fe, Co, Ni) ions occupy the A sites under the tetrahedral symmetry, while Cr ions occupy mainly the B sites under the octahedral symmetry. These findings show that the structures of $TCr_2O_4$ (T = Fe, Co, Ni) are very close to the normal spinel structures. Based on these findings, it is expected that Jahn-Teller (JT) effects are important in $FeCr_2O_4$ and $NiCr_2O_4$. In contrast, $CoCr_2O_4$ maintains the cubic structure without having the JT distortion since both $Cr^{3+}$ and $Co^{2+}$ ions are non-JT ions. This work suggests that the antiferromagnetic interaction between $Cr^{3+}$ and $T^{2+}$ ions plays an important role in determining the magnetic properties of $TCr_2O_4$ (T = Fe, Co, Ni).

Electronic Structure and Properties of High-Tc Superconductor Y-Ba-Cu-O. 1. Oxygen-deficiency in the $YBa_2Cu_3O_x $Superconductor ($6{\leq}{\times}{\leq}7$)

  • U-Hyon Paek;U-Sung Choi;Kee-Hag Lee;Chang-Hong Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.504-509
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    • 1989
  • The effect of oxygen-deficiency on the charge distributions and orbital energies for small copper oxide clusters representing the superconducting materials $YBa_2Cu_3O_x (6{\leq}x{\leq}7)$ were investigated by the extended Huckel molecular orbital (EHMO) method with the tight-binding model. Our calculations show +3 oxidation state of Cu(1) in the $CuO_3$ chain and +2 or +1 of Cu(2) in the $CuO_2$ layers for $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 (or +5), while for $YBa_2Cu_3O_6$ +1 oxidation state of Cu(1) and +3 (or +2) of Cu(2) in the $CuO_2$ layers with the nominal charge of $Cu_3$ = +7 (or +5). For $Cu_3O_{12}$ cluster representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 the Cu(2) $d_{{x^2}-{y^2}}$ orbitals in the $CuO_2$ layers is a typical Jahn-Teller $d^9$ system with the partial hole and the Cu(1) $d_{{_z2}-{_y2}}$ orbital in the $CuO_3$ chain contains hole occupancy. For $Cu_3O_{10}$ cluster representing $YBa_2Cu_3O_6$ with the nominal charge of Cu = +5 the orbital character of the highest partially occupied MO (HPOMO) and the lowest completely unoccupied MO (LCUMO) of $Cu_3O_{12}$ representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 is reversed, and the character of Cu(1) $d{{x^2}-{y^2}}$ orbital of LCUMO of the $Cu_3O_{12} $cluster is vanished. It is suggested that the local crystal field environment of Cu(1) by the oxygens in the Cu(1) chain may play a vital role in conductivity and superconductivity, either alone or through cooperative electronic coupling with the Cu(2) layers in $YBa_2Cu_3O_7.$.

Biosynthesis of the extracellular enzymes in de novo during the differentiation of Aspergillus niger (검정곰팡이의 형태분화에 따른 세포외성효소의 신생적생합성에 관한 연구)

  • Kim, Jong-Hyup
    • The Korean Journal of Mycology
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    • v.6 no.2
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    • pp.1-10
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    • 1978
  • In de novo biosynthesis of the extracellulor enzymes-proteinsaes, alpha and gluc-amylases during the synchronized differentiation of Aspergillus niger in submerged culture and surface liquid culture were investigated. Gluc-amylase was synthesized in the stage of presporulation in which phialide formation is involved. Proteinase was synthesized both in the stages of conidiophore formation and presporulation. Alpha-amylase was synthesized during presporulation and sporulation stages, the activity of enzyme lasted for seven days on surface liquid culture. It seemed that the synthesis was occured in de novo partly repressed by the catabolite, and its nature was found to be constitutive since it is produced in non-starch medium. Polyacrylamide gel electrophoresis have shown that presporulating and sporulating body produced diverse types of the proteins whereas the earlier stages of vegetative body showed simpler profiles. The uptake of C-14 uracil into RNA and C-14 glutamate into protein were shown to be vigorous in presporulating body rather than those in sporulating body. Coincidence of alpha-amylase biosynthesis in de novo and sporulation may be significant in the study of differentiation in which gene expression is involved.

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Chemical and Optical Absorption Spectroscopic Study of Colored Tourmalines (유색 전기석의 화학적 및 광학흡수 분광학적 연구)

  • Kim, Hee-Jong;Kim, Soo-Jin
    • Journal of the Mineralogical Society of Korea
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    • v.6 no.1
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    • pp.1-16
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    • 1993
  • The chemical and optical absorption spectroscopic characters of pink and colorless tourmalines from San Diego mine in California, U.S.A., blue/green tourmalines from anonymous mine, Brazil, and brownis black tourmalines from Uncheon and Haksan mines in Korea have been studied using X-ray diffractometer, electron microprobe, optical absorption spectroscopy, and heat treatment. Least-squares refinements give unit cell diminsions : a = 15.96-16.01 ${\AA}$, c = 7.15-7.16 ${\AA}$ for the brownish black tourmalines, a = 15.82 - 15.87 ${\AA}$, c = 7.09 - 7.10 ${\AA}$ for pink tourmalines, and a = 15.88 - 15.94 ${\AA}$, c = 7.12 - 7.15 ${\AA}$ for blue green tourmalines. The colors of tourmalines are responsible for the transition elements. The pink color is attributed to the $Mn^{3+}$ ions, the blue-green to $Fe^{2+}$ and $Mn^{2+}$, bluish green to $Cu^{2+}$, and the brownish black to $Fe^{2+}$, $Fe^{2+}$ - $Fe^{3+}$, and $Fe^{2+}$ - $Ti^{4+}$. The $Mn^{3+}$ ions of pink color tourmalines are stabilized in the Y sites compressed along the O(1)H-O(3)H axis by Jahn-Teller distortion. Heating removes the pink or red component from tourmalines, producing the colorless stones from the pink and red ones. The bluish green samples change into the greenish blue ones and a certain yellowish green samples change into the light green ones by heat treatment. In the elbaite-schorl series, the concentration of Fe and Mn are variable depending on the color zones. The green zone is characterrized by the high content of Fe and Mn are variable depending on the color zones. The green zone is characterized by the high content of Fe, whereas the pink zone by the high content of Mn. Mn increases in deep yellow zone compared with yellow or colorless zones.

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