• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.674-678
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• 1991

Methanolysis of a ${\beta}$-lactam ring of a cephalosporin was simulated with AM1 semiempirical quantum mechanical calculation. The tetrahedral intermediate TD1 from an O-protonated cephalosporin and a methanol transfers the proton intramolecularly to the C-4 carboxylate to generate an oxyanion, i.e., second tetrahedral intermediate TD2, which undergoes the amide bond cleavage without further protonation on the N-5. For this cleavage a low-energy barrier TS2 was located. According to the energy diagram, tetrahedral intermediates easily undergo ring cleavage even without the protonation on the amide nitrogen.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.743-749
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• 1997

Local structure refinement of the BaFe1-xSnxO3-y system (x=0.00-0.50) has been carried out with Fe K-edge x-ray absorpion spectroscopic studies. It is found out that the Fe ions are placed in two different symmetric sites such as tetrahedral and octahedral sites in the compounds by comparison with Fe K-edge x-ray absorption near edge structure (XANES) spectrum of the γ-Fe2O3 compound as a reference. Small absorption peaks of dipole-forbiden transitions appear at a pre-edge region of 7111 eV due to the existence of Fe ions in the tetrahedral and octahedral sites. The peak intensity decreases with the substitution amount of Sn ion. Three different absorption peaks of 1s→4p dipole-allowed transition appear on the energy region between 7123 and 7131 eV. The peaks correspond to 1s→4p main transition of Fe ions in tetrahedral and octahedral sites and 1s→4p transition followed by the shakedown process of ligand to metal charge transfer. The bond distances between Fe ions in the tetrahedral site and nearest neighboring oxygen atom (Fe-4O), and those in octahedral site (Fe-6O) are determined with the extended x-ray absorption fine structure (EXAFS) analysis. Two different interatomic distances increase with the substitution amount of Sn ion and also the bond lengths of Fe-4O are shorter than those of Fe-6O in all compounds.

• Journal of Magnetics
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• v.10 no.1
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• pp.23-27
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• 2005

The crystallographic and magnetic properties of a series of substitutions in nickel ferrite where the Fe³⁺ is replaced with In³⁺ have been investigated using X-ray diffraction (XRD) and Mössbauer spectroscopy. Information on the exact crystalline structure, lattice parameters, bond lengths and bond angles were obtained by refining their XRD profiles by a Rietveld method. All the crystal structures were found to be cubic with the space group Fd/3m. The lattice constants increased with In³⁺ concentration. The expansion of the tetrahedron was outstanding, indicative of the tetrahedral (A) site preference of larger indium ion. The Mossbauer spectra showed two sets of sextuplet originating from ferric ions occupying the tetrahedral sites and the octahedral (B) sites under the Neel temperature T_N. Regardless of the composition x, the electric quadrupole splitting was zero within the experimental error. At x = 0.2, the magnetic hyperfine fields increased slightly, which meant that the nonmagnetic indium ions occupied preferentially the A-site. At the same time, the intensity of the B-site sub-spectra decreased markedly at the elevated temperature, indicating that the occupation of the A site by indium induced a considerable perturbation on the B site.

• Journal of the Korean Magnetic Resonance Society
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• v.8 no.2
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• pp.70-76
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• 2004

ZORA-DFT calculations of $^{11}$B EFG (electric field gradient) tensors for lithium borates, LiB$_3O_5$ (LBO) and Li$_2B_4O_7$ (LTB), were performed. The calculated values of 11B quadrupole coupling constant and asymmetry parameter are in good agreement with the experimental values. The sign of the quadrupole coupling constant for the tetrahedral boron site was deduced from the distortion from the ideal tetrahedral symmetry.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.378-378
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• 2010

We report the electronic structure of CoFeO-R (R=Hf, La, Nb) thin films studied by x-ray absorption spectroscopy (XAS). These ferrites thin films were prepared by pulsed laser deposition method and characterized by XAS measurements at O K-, Co and Fe L-edges. The O K-edge spectra suggest that there is a strong hybridization between O 2p and 3d electrons of transition metal cations and Fe $L_{3,2}$-edge spectra indicate that Fe-ions exist in $Fe^{2+}$ with tetrahedral site of the spinel structure. Divalent Co ions is also distributed in tetrahedral site with rare earth ions goes to octahedral sites of spinel structure. X-ray magnetic circular dichroism (XMCD) is also used to explain the symmetry and magnetic nature dependence on rare-earth ions.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.2
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• pp.122-129
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• 2005

The characteristics of hydrogen storage have been investigated in the Ti-Cr-Mo and Ti-Cr-V ternary alloys with bcc structure. The alloys were melted by arc furnace and remelted 4-5 times for homogeneity. The lattice parameters, microstructures and phases of the alloys were examined by SEM, EDX and XRD, and the Pressure-Composition isotherms of the alloys were measured. From these data the relationship of the maximum and effective hydrogen storage capacities vs. chemical composition, lattice parameter and the radius of tetrahedral site were analyzed and discussed. The results showed that all of these alloy, in the range of the this study, had mainly bcc solid solutions with small amount of Ti segregation due to a lower melting point of Ti compared with other elements. Lattice parameters of the alloys were very near to the atomic average values of lattice parameters of the constituent elements. It was also found that maximum hydrogen storage capacities of the Ti-Cr-Mo alloys increased with increasing Ti content and the radius of tetrahedral site but the effective hydrogen storage capacities decreased after showing the maximum. The hydrogen storage capacities of the Ti-Cr-V alloys were almost same even though the V contens were quite different from alloy to alloy and this could be attributed to the almost same Ti/Cr ratio of the alloys. The maximum effective hydrogen storage capacity of the Ti-Cr-Mo alloys was revealed at Ti content of about 40${\sim}$50 at% and radius of tetrahedral site of 0.43${\sim}$0.45 nm. The Ti-Cr-V alloys showed the hydrogen storage capacities of 3.0 wt% and effective hydrogen storage capacities of 1.5 wt%.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4059-4062
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• 2012

The effect of a conductive agent on the structural and electrochemical properties of $Li_4Ti_5O_{12}$(LTO) spinel was investigated through neutron diffraction during Li intercalation and electrochemical measurements. The charging process of LTO is known as transformation of the white $(Li_3)_{8a}[LiTi_5]_{16d}O_{12}$ into a dark-colored $(Li_{3-X})_{8a}[Li_{X+Y}]_{16c}[LiTi_5]_{16d}O_{12}$ by incorporating the inserted Li into octahedral 16c sites, and the Li in tetrahedral 8a sites shifted to 16c sites. The occupancy of the tetrahedral 8a site varied with the existence of carbon in the electrode. Without carbon, the lattice parameter and cell volume of LTO decreased more notably than in the carbon-containing LTO electrode during Li insertion process. These phenomena might be attributed that the Li occupancy of the tetrahedral 8a of the LTO electrode without carbon was less than that of the carbon-containing LTO electrode.

• Journal of Magnetics
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• v.5 no.1
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• pp.16-18
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• 2000

The garnets $Nd_{1-x}Bi_xY_2Fe_5O_{12}$ ($\chi$=0.0, 0.25, 0.5, 0.75 and 1.0) have been studied by x-rays, electron microscopy, ferromagnetic resonance, vibrating sample magnetometer and Mossbauer spectroscopy, Ultra-fine polycrystalline cubic samples have been prepared by a melt-salt routed sol-gel method. The Mossbauer spectra consist of two sets of six-line patterns corresponding to $Fe^{3+}$ at the tetrahedral 24(d) and octahedral 16(a) sites. Magnetic hyperfine fields of $Nd_{0.5}Bi_{0.5}Y_2Fe_5O_{12}$ at 12 K are found to be 548 kOe (octahedral site) and 475 kOe (tetrahedral site), respectively, It is found that Debye temperatures for the tetrahedral and octahedral sites of $Nd_{0.75}Bi_{0.25}Y_2Fe_5O_{12}$ are $\theta_{tet}=436$ K and $\theta_{oct}=285$ K, respectively, The iron ions at both sites are highly covalent ferric. The Nel temperature decreases linearly with Bi concentration, from 630 K fur $\chi$=0.0 to 600 K for $\chi$=1.0, suggesting that the superexchange interaction for the Nd-O-Fe link is stronger than that for the Bi-O-Fe link. As a consequence, the coercivity of $Nd_{1-x}Bi_xY_2Fe_5O_{12}$ drastically decreases and the magnetization remains almost constant as x increases.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.70-75
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• 1997

A wide range (10 < Si/V) of mesoporous vanadium silicate molecular sieves with the MCM-41 structure have been synthesized using vanadyl sulfate as the source of vanadium and characterized by XRD, 51V MAS NMR and 29Si MAS NMR. The increase of the unit cell parameter and the decrease of Q3/Q4 ratio of 29Si spectra with the vanadium content suggest the incorporation of vanadium in the framework of MCM-41 structure. 51V MAS NMR demonstrates that vanadiums in as-synthesized V-MCM-41 are present in the chemical environment of octahedra and octahedral vanadium is decreased and tetrahedral vanadium is increased inversely with raising the calcination temperature. Though the thermal treatment in rotor of hydrated sample resulted in the change from tetrahedral environment to octahedral one and the steaming and the acid treatment affect to the chemical environment of vanadium, the spectrum similar to originally calcined sample is regenerated after recalcination. This indicates that the vanadium is belong to the framework in a relatively exposed site. The best quality XRD pattern of the product of Si/V=27 may be attributable to heterogeneous nucleation mechanism. V-MCM-41's having the Si/V ratio lower than 20 are completely collapsed after calcination.

• Journal of Magnetics
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• v.11 no.1
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• pp.51-54
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• 2006

Variation of magnetic properties through Cr substitution for Co in inverse-spinel $CoFe_2O_4$ has been investigated by vibrating-sample magnetometry (VSM) and conversion electron $M\ddot{o}ssbauer$ spectroscopy (CEMS). $Cr_{x}Co_{1-x}Fe_2O_4$ samples were prepared as thin films by a sol-gel method. The lattice constant of the $Cr_{x}Co_{1-x}Fe_2O_4$ samples was found to remain unchanged, explainable in terms of a reduction of tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$ due to substitution of $Cr^{3+}$ ion into octahedral $Co^{2+}$ site. The existence of the tetrahedral $Fe^{2+}$ ions in $Cr_{x}Co_{1-x}Fe_2O_4$ was confirmed by CEMS analysis. Room-temperature magnetic hysteresis curves for the $Cr_{x}Co_{1-x}Fe_2O_4$ films measured by VSM revealed that the saturation magnetization $M_s$ increases by Cr doping. The $M_s$ is maximized when x = 0.1 and decreases for higher x but is still bigger than that of $CoFe_2O_4$. The increase of $M_s$ can be explained partly by the reduction of the tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$.