• Journal of the Mineralogical Society of Korea
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• v.27 no.4
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• pp.271-281
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• 2014

The physicochemical properties of clay minerals have been investigated at the atomistic to nano scale. The microscopic studies are often challenging to perform by using experimental approaches alone. In particular, hydroxyl groups of octahedral sheets in 2:1 clay minerals have been hypothesized to impact the sorption process of metal cations; however, X-ray based techniques alone, a common tool for mineral structure examination, cannot properly test the hypothesis. The current study has examined whether computational mineralogy techniques can be applied to examine the hydroxyl structures of clay minerals. Based on quantum-mechanics and molecular-mechanics computational methods, geometry optimizations were carried out for representative dioctahedral and trioctahedral phyllosilicate minerals. Both methods well reproduced the experimental lattice parameters; however, for structural distortion occurring in the tetrahedral or octahedral sheets, molecular mechanics showed significant deviations from experimental data. The orientation angle of the hydroxyl with respect to (001) basal plane is determined by the balance of repulsion between the hydroxyl proton and Si cations of tetrahedral sites; the quantum-mechanics method predicted $25-26^{\circ}$ for the angle, whereas the angle predicted by the molecular-mechanics method was much higher by $10^{\circ}$ (i.e., $35^{\circ}$). These results demonstrate that computational mineralogy techniques are a reliable tool for clay mineral studies and can be used to further elucidate the roles of hydroxyls in metal sorption process.

• Journal of the Mineralogical Society of Korea
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• v.30 no.4
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• pp.161-172
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• 2017

Clay minerals play a major role in the geochemical cycles of metals in the Critical Zone, the Earth surface-layer ranging from the groundwater bottom to the tree tops. Atomistic scale research of the very fine particles can help understand the fundamental mechanisms of the important geochemical processes and possibly apply to development of hybrid nanomaterials. Molecular dynamics (MD) simulations can provide atomistic level insights into the crystal structures of clay minerals and the chemical reactivity. Classical MD simulations use a force field which is a parameter set of interatomic pair potentials. The ClayFF force field has been widely used in the MD simulations of dioctahedral clay minerals as the force field was developed mainly based on dioctahedral phyllosilicates. The ClayFF is often used also for trioctahedral mineral simulations, but disagreement exits in selection of the interatomic potential parameters, particularly for Mg atom-types of the octahedral sheet. In this study, MD simulations were performed for trioctahedral clay minerals such as brucite, lizardite, and talc, to test how the two different Mg atom types (i.e., 'mgo' or 'mgh') affect the simulation results. The structural parameters such as lattice parameters and interatomic distances were relatively insensitive to the choice of the parameter, but the vibrational power spectra of hydroxyls were more sensitive to the choice of the parameter particularly for lizardite.

• Journal of the Mineralogical Society of Korea
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• v.24 no.3
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• pp.195-204
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• 2011

Exsolution intergrowth of ilmenite and hematite was studied by the Rietveld refinement method. According to the analysis on these two structural analog minerals, it was found that octahedron (M2) of Ti in ilmenite is in the least deformation, then that (M1) of Fe in ilmenite is deformed next, and octaheron deformation of Fe in hematite is between M1 and M2. High pressure compression experiment was performed up to 5.8 GPa, where two minerals' XRD peaks merged completely. Ilmenite shows normal compression behavior, whereas hematite shrinks in very small amount. This kind of abnormal behavior might be due to the differential response to the applied pressure corresponding to the different compressibilities of the minerals each other.

• Proceedings of the Petrological Society of Korea Conference
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• 2003.05a
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• pp.77-79
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• 2003

• Proceedings of the Mineralogical Society of Korea Conference
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• 2003.05a
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• pp.77-79
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• 2003

• Journal of the Mineralogical Society of Korea
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• v.29 no.4
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• pp.209-220
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• 2016

Clay minerals are a major player to determine geochemical cycles of trace metals and carbon in the critical zone which covers the atmosphere down to groundwater aquifers. Molecular dynamics (MD) simulations can examine the Earth materials at an atomic level and, therefore, provide detailed fundamental-level insights related to physicochemical properties of clay minerals. In the current study, we have applied classical MD simulations with clayFF force field to dioctahedral clay minerals (i.e., gibbsite, kaolinite, and pyrophyllite) to analyze and compare structural parameters (lattice parameter, atomic pair distance) with experiments. We further calculated vibrational power spectra for the hydroxyls of the minerals by using the MD simulations results. The MD simulations predicted lattice parameters and interatomic distances respectively deviated less than 0.1~3.7% and 5% from the experimental results. The stretching vibrational wavenumber of the hydroxyl groups were calculated $200-300cm^{-1}$ higher than experiment. However, the trends in the frequencies among different surface hydroxyl groups of each mineral was consistent with experimental results. The angle formed by the surface hydroxyl group with the (001) plane and hydrogen bond distances of the surface hydroxyls were consistent with experimental result trends. The inner hydroxyls, however, showed results somewhat deviated from reported data in the literature. These results indicate that molecular dynamics simulations with clayFF can be a useful method in elucidating the roles of surface hydroxyl groups in the adsorption of metal ions to clay minerals.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.198-205
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• 1979

A valence bond method of calculation of the dipole moments for octahedral $(M(III)0_3S_3)$ type complexes are developed, using $d^2sp^3 $hybrid orbitals of the central metal ions and the single basis set orbital of ligands. (M (III) =V (III), Cr (III), Mn (III), Fe (III), Co (III), Ru (III), Rh (III) and OS (III)). In this method the mixing coefficient of the valence basis sets for the central metal ion with the appropriate ligand orbitals is not required to be the same, differently from the molecular orbital method. The valence bond method is much more easier to calculate the dipole moments for octahedral complexes than the approximate molecular orbital method and the calculated results are also in the range of the experimental vaues.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.5 no.4
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• pp.394-399
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• 1995

Dielectric properties and crystal structure changes with temperature were observed on $(Na_{0.5}Sr_{0.5})(Ti_{0.5}Nb_{0.5})O_{3}$ which had a superstructure due to oxygen octahedron tilting. Dielectric loss peak observed at 380 K was found to have a relation with a primitive cell change from tetragonal to cubic, however, in this case, dielectric constant variation was not observed. Therefore it was found that the dielectric loss was more senstive than the dielectric constant for detecting the structure change. After the structure change of primitive cell from tetragonal to cubic, X-ray diffraction peaks of superstructure, which completely disappear above 500 K, were still observed. And no dielectric property variations were found with the disappearence of superstucture.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.19 no.5
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• pp.246-250
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• 2009

The Ni formation behavior from the reduction of NiO nano crystals in the $H_2/N_2$ gas mixtures. The NiO nano crystals were synthesized by heat-treating nickel nitrate$(Ni(NO_3)_2\cdot6H_O)$ in the air at $500^{\circ}C$, and had an octahedral shape and the particle size of 200~500 nm. The NiO nano-crystals had well-developed (111) planes which is hardly formed in normal synthetic conditions. The reduction process was carried out at 300 and $600^{\circ}C$ for 15 and 60 minutes, respectively. When the NiO nano-crystals were reduced at $300^{\circ}C$, the Ni particles sustained the same octahedral shape as NiO, while Ni particles were to agglomerate at $600^{\circ}C$.

• Journal of the Korean Magnetics Society
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• v.17 no.1
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• pp.30-33
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• 2007

The $FeIn_2S_4$ exhibits an inverse spinel which Fe ions are occupied to the octahedral(B) site, while In ions are occupied to both the tetrahedral(A) and the octahedral(B) site. The $N\'{e}el$ temperature($T_N$) is determined to be 13 K. The effective moment of $FeIn_2S_4$ found to be $5.094{\mu}_B$ from the fit of Curie-Weiss inverse susceptibility for the temperature range over $T_N$, implying angular momentum contribution. The angular momentum contribution is shown in $M\"{o}ssbauer$ spectra for the antiferromagnetic ordering region($T{\leq}\;13K$), too. A weak $Fe^{2+}(B)-S^2-Fe^{2+}(B)$ interaction is responsible for a low $N\'{e}el$ temperature($T_N$) in $FeIn_2S_4$ system. The temperature dependence of electric quadrupole interaction is explained by z-axial crystalline field energy.