• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.574-582
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• 1991

The CO molecules adsorbed on Ni(111) surface is studied in the cluster approximation employing EH method with self-consistent charge iteration. The effect of CO coverage is simulated by allowing the variation of valence state ionization potentials of each Ni atom in model cluster according to the self-consistent charge iteration method. The CO coverage dependent C-O stretching frequency shift, adsorption site conversion, and metal work function change are attributed to the charge transfer between metal surface and adsorbate. For CO/Ni(111) system, net charge transfer from Ni surface to chemisorbed CO molecules makes surface Ni atoms be more positive with increasing coverage, and lowers Ni surface valence band. This leads to a weaker interaction between metal surface valence band and Co $2{\pi}^{\ast}$ MO, less charge transfer to a single CO molecule, and the bule shift of C-O stretching frequency. Further increase of coverage induces the conversion of 3-fold site CO to lower coordination site CO as well as the blue shift of C-O stretching frequency. This whole process is accompanied by the continuous increase of metal work function.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.313-325
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• 2007

In order to have better insights into adsorption of organic molecules on kaolinite surfaces, we performed quantum chemical calculations of interaction between three different model clusters of kaolinite siloxane surfaces and benzyl alcohol, with emphasis on the effect of size and lattice topology of the cluster on the variation of electron density and magnetic shielding tensor. Model cluster 1 is an ideal silicate tetrahedral surface that consists of 7 hexagonal rings, and model cluster 2 is composed of 7 ditrigonal siloxane rings with crystallographically distinct basal oxygen atoms in the cluster, and finally model cluster 3 has both tetrahedral and octahedral layers. The Mulliken charge analysis shows that siloxane surface of model cluster 3 undergoes the largest electron density transfer after the benzyl alcohol adsorption and that of model cluster 1 is apparently larger than that of model cluster 2. The difference of Mulliken charges of basal oxygen atoms before and after the adsorption is positively correlated with hydrogen bond strength. NMR chemical shielding tensor calculation of clusters without benryl alcohol shows that three different basal oxygen atoms (O3, O4, and O5) in model cluster 2 have the isotropic magnetic shielding tensor as $228.2{\pm}3.9,\;228.9{\pm}3.4,\;and\;222.3{\pm}3.0ppm$, respectively. After the adsorption, the difference of isotropic chemical shift varies from 1 to 5.5 ppm fer model cluster 1 and 2 while model cluster 2 apparently shows larger changes in isotropic chemical shift. The chemical shift of oxygen atoms is also positively correlated with electron density transfer. The current results show that the adsorption of benzyl alcohol on the kaolinite siloxane surfaces can largely be dominated by a weak hydrogen bonding and electrostatic force (charge-charge interaction) and demonstrate the importance of the cluster site and the lattice topology of surfaces on the adsorption behavior of the organic molecules on clay surfaces.

• Journal of the Korean Chemical Society
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• v.67 no.5
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• pp.333-338
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• 2023

In this study, the H₂O reaction with SiO clusters was investigated using ab initio Monte Carlo simulations and density functional theory calculations. Three chemistry models, PBE1/DGDZVP (Model 1), PBE1/DGDZVP (Si atom), and aug-cc-pVDZ (O and H atoms), (Model 2) and PBE1/aug-cc-pVDZ (Model 3), were used. The average bond lengths, as well as the relative and reaction energies, were calculated using Models 1, 2, and 3. The average bond lengths of Si-O and O-H are 1.67-1.75 Å and 0.96-0.97 Å, respectively, using Models 1, 2, and 3. The most stable structures were formed by the H transfer from an H₂O molecule except for Si₃O₃-H₂O-1 cluster. The Si₃O₃ cluster with H₂O exhibited the lowest reaction energy. In addition, the Bader charge distributions of the Si_nO_n and (SiO)_n-H₂O clusters with n = 1-7 were calculated using Model 1. We determined that the reaction sites between H₂O and the SiO clusters possessed the highest fraction of electrons.

• Journal of the Institute of Electronics Engineers of Korea SP
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• v.40 no.3
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• pp.203-216
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• 2003

In this paper a new feature extraction and target classification method is proposed for the recognition part of FLIR(Forwar Looking Infrared)-image-based ATR system. Proposed feature extraction method is "cluster(=set of classes)-based"version of previous fisherfaces method that is known by its robustness to illumination changes in face recognition. Expecially introduced class clustering and cluster-based projection method maximizes the performance of fisherfaces method. Proposed target image classification method is based on the mixture of experts model which consists of RBF-type experts and MLP-type gating networks. Mixture of experts model is well-suited with ATR system because it should recognizee various targets in complexed feature space by variously mixed conditions. In proposed classification method, one expert takes charge of one cluster and the separated structure with experts reduces the complexity of feature space and achieves more accurate local discrimination between classes. Proposed feature extraction and classification method showed distinguished performances in recognition test with customized. FLIR-vehicle-image database. Expecially robustness to pixelwise sensor noise and un-wanted intensity variations was verified by simulation.

• 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 $YBa_2Cu_3O_7.$.

• The Korean Journal of Ceramics
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• v.3 no.1
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• pp.5-12
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• 1997

Charged carbon clusters which are formed by the gas activation are suggested to be responsible for the formation of the metastable diamond film. The number of carbon atoms in the cluster that can reverse the stability between diamond and graphite by the capillary effect increases sensitively with increasing the surface energy ratio of graphite to diamond. The gas activation process produces charges such as electrons and ions, which are energetically the strong heterogeneous nucleation sites for the supersaturated carbon vapor, leading to the formation of the charged clusters. Once the carbon clusters are charged, the surface energy of diamond can be reduced by the electrical double layer while that of graphite cannot because diamond is dielectric and graphite is conducting. The unusual phenomena observed in the chemical vapor deposition diamond process can be successfully approached by the charged cluster model. These phenomena include the diamond deposition with the simultaneous graphite etching, which is known as the thermodynamic paradox and the preferential formation of diamond on the convex edge, which is against the well-established concept of the heterogeneous nucleation.

• The Korean Journal of Ceramics
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• v.5 no.2
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• pp.131-136
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• 1999

Yttria stabilized zirconia(YSZ) films were deposited on porous NiO substrates and quartz plates by the thermal CVD using $ZrCl_4, YCl_3$ as precursors, and $O_2$ as a reactive gas at atmospheric pressure. The evaporation temperature of $ZrCl_4$ was varied from $250^{\circ}C$ to $550^{\circ}C$ while the temperatures of $YCl_3$ and the substrate were varied from $1000^{\circ}C$ to $1030^{\circ}C$. As the evaporation temperature of $ZrCl_4$ increased, the deposition rate of $ZrO_2$ decreased, contrary to our expectation. As a result of the decreased deposition rate of $ZrO_2$, the yttria content increase. The high evaporation temperature of $ZrCl_4$ makes the well-faceted crystal while the low evaporation temperature leads to the cauliflower-shaped structure. The dependence of the evaporation temperature on the growth rate and the morphological evolution was interpreted by the charged cluster model.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.132-137
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• 1993

The electronic structure of two dimensional layered compound, FeOCl, is studied with the band model and the cluster model approximation employing Extended-Huckel (EH) method. We examine the effects of intercalation (e.g., localization of transferred electron, conductivity increase). FeOCl has the electronic structure typical for layered compounds as expected. For FeOCl-$Li_{1/2}$ system, the charge transfer from Li to the FeOCl lattice occurs, and electrons are built up almost exclusively on Fe atoms. The partially filled band of FeOCl-$Li_{1/2}$ complex is responsible for the increase in conductivity.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.3
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• pp.289-294
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• 1999

The charged clusters or particles, which contain hundreds to thousands of atoms or even more, are suggested to from in the gas phase in the thin film processes such as CVD, thermal evaporation, laser ablation, and flame deposition. All of these processes are also phase synthesis of the nanoparticels. Ion-induced or photo-induced nucleation is the main mechanism for the formation of these nanoclusters or nanoparticles in the gas phase. Charge clusters can make a dense film because of its self-organizing characteristics while neutral ones make a porous skeletal structure because of its Brownian coagulation. The charged cluster model can successfully explain the unusual phenomenon of simultaneous deposition and etching taking place in diamond and silicon CVD processes. It also provides a new interpretation on the selective deposition on a conducting material in the CVD process. The epitaxial sticking of the charged clusters on the growing surface is getting difficult as the cluster size increases, resulting in the nanostructure such as cauliflower or granular structures.

• Korean Journal of Crystallography
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• v.14 no.1
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• pp.16-23
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• 2003

The electronic structure and chemical bonding of β-MnO₂ were theoretically investigated by DV-X/sub α/ (the discrete variation X/sub α/) method. which is a sort of the first principle molecular orbital method using Hatre-Fock-Slater approximation. The calculations on several cluster models having different sizes were carried out for the determination of a model suited for analyzing bulk state. The Mn/sub 15/O/sub 56/ model was selected as a sufficiently suitable model for the calculation of electronic state and chemical bonding by the comparison of the calculated XPS (X-ray photo-electron spectrum) and experimentally measured XPS. By using this model, the electron energy level, the density of state, the bond overlap population, the charge density distribution, and the net ionic transfer between cations and anions were calculated and discussed.