• Bulletin of the Korean Chemical Society
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• 제27권9호
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• pp.1405-1417
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• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

• 대한환경공학회지
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• 제31권2호
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• pp.125-131
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• 2009

영가철과 혐기성 미생물을 이용한 환원적 탈염화반응을 통한 다이옥신 처리 능력을 평가하기 위해, 자유에너지 선형관계(linear free energy relationship)를 이용하여 다이옥신의 탈염화에 의한 농도 및 독성변화 예측 모델을 최초로 정립하였다. 수용액상에 존재하는 다이옥신류의 깁스자유에너지는 기존 문헌의 열역학적 계산결과를 범밀도함수이론(density functional theory)을 이용한 계산 수준으로 보정하였으며, 보정된 깁스자유에너지와 실험을 통해 얻은 탈염화 반응속도 상수와의 선형관계를 통해 다이옥신의 탈염화 반응 256개에 대한 반응속도상수를 예측하였다. 본 모델을 통해 탈염화에 의해 변화하는 다이옥신 류 76종에 대한 시간 별 농도를 계산할 수 있다. 8염화다이옥신(Octachlorinated dibenzo-p-dioxin, OCDD)이 완전히탈염화되어 dibenzo-p-dioxin (DD)로 탈염화되기까지는 100년 이상의 반응시간이 필요하였으며, 독성등가값(toxic equivalent quantity, TEQ)의 경우 탈염화가 진행되면서 초기농도의 10배 이상까지 증가하는 것으로 밝혀졌다. 이를 통해, 다이옥신의 처리를 위해서는 좀 더 빠른 탈염화 반응속도를 갖는 다른 전자공여 시스템을 사용하거나, 환원적 탈염화-라디칼 산화와 같은 복합 연계처리가 필요함을 알 수 있다. 본 논문을 통해 제시된 예측 기법은 다이옥신뿐 아니라 다른 할로겐화 화합물의 탈염화 예측과 여러 전자공여 시스템에 대한 평가에 적용이 가능하다.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.2889-2894
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• 2013

A new complex [$Ni(phen)(C_9H_8Br_2NO_3)_2{\cdot}2CH_3OH{\cdot}2H_2O$] [phen: 1,10-phenanthroline $C_9H_8Br_2NO_3$: 3,5-dibromo-L-tyrosine] was synthesized and characterized by IR, elemental analysis and single crystal X-ray diffraction. X-ray crystallography shows that Ni(II) ion is six-coordinated. The Ni(II) ion coordinates with four nitrogen atoms and two oxygen atoms from three ligands, forming a mononuclear Ni(II) complex. The crystal crystallizes in the Orthorhombic system, space group $P2_12_12$ with a = 12.9546 ${\AA}$, b = 14.9822 ${\AA}$, c = 9.9705 ${\AA}$, V = 1935.2 ${\AA}$, Z = 1, F(000) = 1008, S = 0.969, ${\rho}_{calcd}=1.742g{\cdot}cm^{-3}$, ${\mu}=4.688mm^{-1}$, $R_1$ = 0.0529 and $wR_2$ = 0.0738 for 3424 observed reflections (I > $2{\sigma}(I)$). Theoretical study of the title complex was carried out by density functional theory (DFT) method and the B3LYP method employing the $6-3l+G^*$ basis set. The energy gap between HOMO and LUMO indicates that this complex is prone to interact with DNA. CCDC: 908041.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.139-139
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• 2012

With angle resolved photoemission spectroscopy (ARPES), the surface electronic band structures of Pt3Co (111) and Pt3Ni (111) single crystals are investigated, which allow to study the bonding interaction between chemically absorbed atomic oxygen and its surfaces. The d-band electrons of subsurface TM are separated from the direct chemical bonding with atomic oxygen. That is, the TM does not contribute to direct chemical bonding with oxygen. From the density functional theory (DFT) calculations, it is identified that the main origin of improved oxygen absorption property, i.e. softening of Pt-O bonding, is due to the suppression of Pt surface-states which is generated from change of interlayer potential, i.e. charge polarization, between Pt-top and TM-subsurface. Our results point out the critical roles of subsurface TM in modifying surface electronic structures, which in turn can be utilized to tune surface chemical properties.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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• pp.55-55
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• 2003

Ferroelectric 물질은 고유전성, 자발분극과 전기장에 따른 유전상수의 변화 등의 특성을 가지고 있으므로 많은 연구가 진행중이다. 이러한 ferroelectric 물질의 유전 특성에 미치는 요소로는 물질의 조성비, 박막의 스트레스, 결정성 등이 있다. 특히 스트레스에 대한 연구가 활발히 진행중이다. 본 연구에서 산화물 인공격자를 이용하여 단일박막에서 얻을 수 없는 격자변형도를 얻어 격자 변형이 박막의 유전특성에 미치는 영향을 연구하였다. BaTiO$_3$ (BTO)/SrTiO$_3$ (STO) 산화물 인공격자를 Pulsed laser deposition (PLD)법으로 (La,Sr)CoO$_3$ 전극이 코팅된 MGO (100) 단결정 기판위에 증착시켰다. 적층 주기에 변화를 주어 BTO와 STO 각각 1.01~1.095와 0.925 ~ 1.003의 단일 막에서는 얻을 수 없는 격자 변형도를 얻었다. 이 실험적 데이터를 기초로 하여 density functional theory (DFT)라고 불리는 범함수밀도론를 기초한 제일원리적 계산 방법을 통하여 격자 변형된 SrTiO$_3$의 구조적, 전기적 특성을 계산하였다. SrTiO$_3$와 BaTiO$_3$ 격자의 안정성을 분석하기 위하여 Vienna Ab-intio Simulation Package (VASP) code가 사용되었다. SrTiO$_3$와 BaTiO$_3$ 산화물 격자의 안정성 분석 후, frozen-phonon 계산 방법을 사용하여 zone-centered optical phonon mode가 계산되었으며, mode effective charge는 Berry-phase polarization 으로부터 얻어졌다. SrTiO$_3$ 격자가 격자변형이 일어나지 않은 상태로부터 c/a= 0.985로 격자 변형 이 일어남에 따라 optical phonon mode는 점차 hardening되었다. BaTiO$_3$ 격자의 경우 SrTiO$_3$ 격자와는 달리 격자 변형이 1.01~1.023으로 진행됨에 따라 optical phonon mode의 증가를 가져왔으나 Born effective charge의 증가하였으며, 더 이상 격자 변형이 진행됨에 따라 optical phonon mode의 감소를 가져왔으나 Born effective charge의 증가 유전상수는 증가했다. 격자 변형이 SrTiO$_3$ 와 BaTiO$_3$ 산화물 격자의 optical phonon mode와 Born effective charge에 크게 영향을 미쳤다.

• Smart Structures and Systems
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• 제8권1호
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• pp.17-37
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• 2011

The microcantilever (MCL) sensor is one of the most promising platforms for next-generation label-free biosensing applications. It outperforms conventional label-free detection methods in terms of portability and parallelization. In this paper, an overview of recent advances in our understanding of the coupling between biomolecular interactions and MCL responses is given. A dual compact optical MCL sensing platform was built to enable biosensing experiments both in gas-phase environments and in solutions. The thermal bimorph effect was found to be an effective nanomanipulator for the MCL platform calibration. The study of the alkanethiol self-assembly monolayer (SAM) chain length effect revealed that 1-octanethiol ($C_8H_{17}SH$) induced a larger deflection than that from 1-dodecanethiol ($C_{12}H_{25}SH$) in solutions. Using the clinically relevant biomarker C-reactive protein (CRP), we revealed that the analytical sensitivity of the MCL reached a diagnostic level of $1{\sim}500{\mu}g/ml$ within a 7% coefficient of variation. Using grazing incident x-ray diffractometer (GIXRD) analysis, we found that the gold surface was dominated by the (111) crystalline plane. Moreover, using X-ray photoelectron spectroscopy (XPS) analysis, we confirmed that the Au-S covalent bonds occurred in SAM adsorption whereas CRP molecular bindings occurred in protein analysis. First principles density functional theory (DFT) simulations were also used to examine biomolecular adsorption mechanisms. Multiscale modeling was then developed to connect the interactions at the molecular level with the MCL mechanical response. The alkanethiol SAM chain length effect in air was successfully predicted using the multiscale scheme.

• 한국세라믹학회지
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• 제46권6호
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• pp.695-699
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• 2009

We studied the transfer of oxygen vacancy and proton in Y-doped BaZr$O_3$ (BYZ) using density functional theory (DFT). An oxygen vacancy was generated in the $2{\times}2{\times}2$ BYZ superstructure by replacing two Zr atoms with two Y atoms to satisfy the charge neutrality condition. The O vacancy transfer between the first and second nearest O atom sites from a Y atom showed the lowest activation energy barrier of 0.42 eV, compared to the other transfers between first and first, and second and second in the superstructure. Two protons were inserted in the structure by adding a proton and hydroxyl that were supplied by the dissociation of a water molecule. The two protons bonded to the first and second nearest O atoms were energetically the most favorable. The activation energy barrier for a proton transfer in the structure was 0.51 eV, when either proton transferred to its neighbor O atom. This value was well matched with the experimentally determined one.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2010년도 제39회 하계학술대회 초록집
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• pp.145-145
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• 2010

In this paper, we report that the effects of hydrogen doping on the electrical and optical properties of typical transparent conducting oxide films such as ZnO and $SnO_2$ prepared by magnetron sputtering. Recently, density functional theory (DFT) calculations have shown strong evidence that hydrogen acts as a source of n-type conductivity in ZnO. In this work, the beneficial effect of hydrogen incorporation on Ga-doped ZnO thin films was demonstrated. It was found that hydrogen doping results a noticeable improvement of the conductivity mainly due to the increases in carrier concentration. Extent of the improvement was found to be quite dependent on the deposition temperature. A low resistivity of $4.0{\times}10^{-4}\;{\Omega}{\cdot}cm$ was obtained for the film grown at $160^{\circ}C$ with $H_2$ 10% in sputtering gas. However, the beneficial effect of hydrogen doping was not observed for the films deposited at $270^{\circ}C$. Variations of the electrical transport properties upon vacuum annealing showed that the difference is attributed to the thermal stability of interstitial hydrogen atoms in the films. Theoretical calculations also suggested that hydrogen forms a shallow-donor state in $SnO_2$, even though no experimental determination has yet been performed. We prepared undoped $SnO_2$ thin films by RF magnetron sputtering under various hydrogen contents in sputtering ambient and then exposed them to H-plasma. Our results clearly showed that the hydrogen incorporation in $SnO_2$ leads to the increase in carrier concentration. Our experimental observation supports the fact that hydrogen acting as a shallow donor seems to be a general feature of the TCOs.

• 반도체디스플레이기술학회지
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• 제8권2호
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• pp.55-58
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• 2009

Density functional theory was used to investigate the adsorption and reaction of $HfCl_4$ with two hydroxyls on Si (001)-$2{\times}1$ surface in atomic layer deposition (ALD) process. We prepared a reasonable Si substrate which consisted of six inter-dimer dissociated $H_2O$ molecules and two intra-dimer dissociated $H_2O$ molecules. The $HfCl_4$must react with two hydroxyls to be a bulk-like structure. When $HfCl_4$ was adsorbed on a hydroxyl, there was energy benefit of -0.55 eV. Though there was energy loss for $HfCl_4$ to react with H of hydroxyl, thermal energy of ALD chamber would be enough to pass the energy barriers. There were five reaction pathways for $HfCl_4$ to react with two hydroxyls; inter-dimer, intra-dimer, cross-dimer, inter-row, and cross-row. Inter-row, inter-dimer and intra-dimer were relatively favorable among the five reaction pathways based on the energy difference. The electron densities between O and Hf in these three reactions were higher than the others and they had shorter Hf-O and O-O bond lengths than the other two reaction pathways.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.237-253
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• 2022

The methyl 2-(1,3-dithietan -2- ylidene)-3-oxobutanoate (MDYO) and 2-(1,3-dithietan-2-ylidene) cyclohexane -1,3-dione (DYCD) were synthesized and tested at various concentrations as corrosion inhibitors for 316L stainless steel in 1 M HCl using weight loss, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), surface analysis techniques (SEM / EDX and Raman spectroscopy) and Functional Density Theory (DFT) was also used to calculate quantum parameters. The obtained results indicated that the inhibition efficiency of MDYO and DYCD increases with their concentration, and the highest value of corrosion inhibition efficiency was determined in the range of concentrations investigated (0.01 × 10^-3 - 10^-3 M). Polarization curves (Tafel extrapolation) showed that both compounds act as mixed-type inhibitors in 1M HCl solutions. Electrochemical impedance spectra (Nyquist plots) are characterized by a capacitive loop observed at high frequencies, and another small inductive loop near low frequencies. The thermodynamic data of adsorption of the two compounds on the stainless steel surface and the activation energies were determined and then discussed. Analysis of experimental results shows that MDYO and DYCD inhibitors adsorb to the metal surface according to the Langmuir model and the mechanism of adsorption of both inhibitors involves physisorption. SEM-EDX results confirm the existence of an inhibitor protective film on the stainless steel surface. The results derived from theoretical calculations supported the experimental observation.