• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.14-24
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• 1987

The CNDO/2 method has been used to calculate the electronic structure of the zeolites and silicas, and to investigate the interaction of CO molecules with the OH groups or the exchanged cation in the zeolites. The interaction energies of CO molecules with OH groups in silica were ca. 12kcal/mol, the bond distance, R(O-H${\cdots}$C) was 2.6${\AA}$. The strength of bond between CO molecules and various types of cations in the zeolites was in the following order: $H^+ < Na^+ < Li^+$, i.e., this increased with increasing electrostatic field of cations. The bond orders of CO molecules interacting with the OH groups or the cations increased but for the OH-OC type interaction. The theoretical decationization energies of exchanged cations in the zeolites decreased in the order: $H^+ > Li^+ > Na^+$. And these energies depended on the amount of charge density transfered from the skeleton to the cations in order to compensate its negative charge.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1945-1950
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• 2011

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

• Proceedings of the KIEE Conference
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• 1999.11d
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• pp.848-850
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• 1999

In this study, PZT etching was performed using planar inductively coupled Ar(20)/$Cl_2/BCl_3$ plasma, The etch rate of PZT film was 2450 $\AA/min$ at Ar(20)/$BCl_3$(80) gas mixing ratio and substrate temperature of $80^{\circ}C$. X-ray photoelectron spectroscopy (XPS) analysis for film composition was utilized. The chemical bond of PbO is broken by ion bombardment, and the peak of metal Pb in a Pb 4f peak begins to appear upon etching, decreasing Pb content faster than Zr and Ti. As increase content of additive $BCl_3$, the relative content of oxygen decreases rapidly. We thought that abundant Band BCl radicals made volatile oxy-compound such as $B_{x}O_{y}$ and/or $BClO_x$ bond. To understand etching mechanism, Langmuir probe and optical emission spectroscopy (OES) analysis were utilized for plasma diagnostic.

• Bulletin of the Korean Chemical Society
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• v.8 no.5
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• pp.372-376
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• 1987

Acetone solution of quinoline-8-carbaldehyde reacts with $[Rh(cod)(PPh_3)_2] PF_6$and $[Ir(cod)(PPh_3)_2] PF_6$ to yield $[Rh(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (1) and $[Ir(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (2), respectively. The compound $[Ir(cod)(PPh_3)_2] PF_6$ also reacts with $Ph_2PC_6H_4-o-CHO$ in the acetone / $H_2O$ mixture to give $[Ir(Ph_2PC_6H_4-o-CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (3). Compounds 1, 2, and 3 were characterized by infrared, $^1H$ NMR, $^{31}P$ NMR spectra and conductivity measurement. The $^1H$ NMR spectra of 1, 2, and 3 support the presence of a terminal hydride that is cis to the phosphine. The IR band of 3 at 2185 $cm^{-1}$, which is assigned to $\nu$(Ir-H), and the hydride cleavage reaction of 3 with $CCl_4$, provide evidence for the Ir-H bond.

• Journal of Photoscience
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• v.12 no.3
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• pp.185-186
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• 2005

The electronic structure of photoskinsensitizing psoralens has been investigated by the ab initio calculations. The photocycloaddition reaction of 8-methoxypsoralen with thymine is studied as a model for the photosensitizing reaction of psoralen with DNA bases. The photocycloadduct was inferred to be a C4-cycloaddition product with the stereochemistry of Syn, H-H, Syn, H-T formed through [2+2] addition reaction between the 3,4-double bonds of 8-methoxypsoralen and 5,6-double bond of thymine base.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.397-397
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• 2013

The electrical, electronic, optical properties and the local structure of Nickel Oxide (NiO) thin film have been investigated by X-ray photoelectron spectroscopy (XPS), Reflection Electron Energy Loss Spectroscopy (REELS), UV-spectrometer,Hall Effect measurement and X-ray absorption spectroscopy (XAS). The XPS results show that the Ni 2p spectra for all films consist of $Ni2p_{3/2}$ at around 854.5 eV which indicate the presence of Ni-O bond from NiO phase and for the annealed film at temperature above $200^{\circ}C$ shows the coexist Ni oxide and Ni metal phase. The REELS spectra showed that the band gaps of the NiO thin films were abruptly decreased with increasing temperature. The values of the band gaps are consistent with the optical band gaps estimated by UV-Spectrometer. The optical transmittance spectra shows that the transparency of NiO thin films in the visible light region was deteriorated with higher temperature due to existence of $Ni^0$. Hall Effect measurement suggest that the NiO thin films prepared at relatively low temperatures (RT and $100^{\circ}C$) are suitable for fabricating p-type semiconductor which showed that the best properties was achieved at $100^{\circ}C$, such as a low resistivity of $7.49{\Omega}.cm$. It can be concluded that the annealing process plays a crucial role in converting from p type to n type semiconductor which leads to reducing electrical resistivity of NiO thin films. Furthermore, the extended X-ray absorption fine structure (EXAFS) spectrum at the Ni K-edge was used to address the local structure of NiO thin films. It was found that the thermal treatments increase the order in the vicinity of Ni atom and lead the NiO thin films to bunsenite crystal structure. Moreover, EXAFS spectra show in increasing of coordination number for the first Ni-O shell and the bond distance of Ni-O with the increase of substrate temperature.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.654-660
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• 1998

$[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.43 no.2 s.344
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• pp.13-17
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• 2006

Pentacene channel for organic thin film transistor was deposited on the SiOC film by thermal evaporation. The growth of pentacene is related with the Diels-Alder reaction and the nucleophilic reaction by the thermal induction. The surface is an important factor to control the recursive Diels-Alder reaction for growing of pentacene on SiOC far The terminal C=C double bond of pentacene molecule was broken easily as a result of attack of the nucleophilic reagents on the surface of SiOC film. The nucleophilic reaction can be accelerated by increasing temperature on surface, and it maks pentacene to grow hardly on the SiOC film with a flow rate ratio of $O_2/(BTMSM+O_2)=0.5$ due to its inorganic property. The nucleophlic reaction mechanism is $SN_2(bimolecular nucleophilic substitution)$ type.

• Journal of the Korean Chemical Society
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• v.57 no.4
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• pp.447-454
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• 2013

In this research, two new complexes of N-(2-aminoethyl)-1,3-propanediamine (aepn), $[Cd(aepn)_2]I_2$ (1) and $[Cd(aepn)_2]Cl_2{\cdots}H_2O$ (2), were prepared and identified by elemental analysis, FT-IR, Raman spectroscopy and single-crystal X-ray diffraction. Geometry around the cadmium atom in two complexes by coordination of six nitrogen atoms of two aepn is distorted octahedral. If distortion in the mer-$[Cd(aepn)_2]^{2+}$ cation is disregarded, it has a $C_2$ axis and $C_2$ symmetry. The cyclic voltammetry experiments were carried out to study the complexation process. Two structural surveys on coordination modes and complexes of aepn are presented. A study was carried out using CSD data to estimate the averages of bond lengths for different types of the Cd-N bonds. It was found that the intermolecular $N-H{\cdots}I$, $C-H{\cdots}I$ hydrogen bonds in 1 and $N-H{\cdots}Cl$, $N-H{\cdots}O$, $C-H{\cdots}O$, $O-H{\cdots}Cl$ in 2 stabilized the crystal networks.

• Korean Journal of Materials Research
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• v.8 no.6
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• pp.538-544
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• 1998

The spallation of a thermal barrier coating layer depends on the formation of brittle spinels. thermal expansion mismatch between ceramic and metal. the phase transformation of a ceramic layer and residual stress of coating layer. In this work. the formation mechanism of oxide scale formed by oxidation treatment at 90$0^{\circ}C$ was investigated in order to verify oxidation behavior at the interface between E-beam coated $Zr0_2$-7wt.% $Y_20_3$ and plasma sprayed CoNiCrAIY. Some elements distributed in the bond coating layer were selectively oxidized after oxidation. At the initial time of oxidation. AI-depletion zone and $\alpha$-$Al_O_3$,O, were formed at the bond coating layer by the AI-outward diffusion. After layer grew until critical thickness. spinels. $Cr_20$, and $C0_2CrO_4$ by outward diffusion of Co. Cr, Ni were formed. It was found that the formation of spinels may be related to the spallation of $Zr0_2$-7wt.% $Y_20_3$ during isothermal oxidation.