• Applied Science and Convergence Technology
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• 제25권1호
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• pp.19-24
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• 2016

In this study, we evaluated the change of electronic structure during redox process in cerium-doped $ZrO_2$ grown by sol gel method. By sol-gel method, we could obtain cerium-doped $ZrO_2$ in high oxygen partial pressure and low temperature. After post annealing process in nitrogen ambient, the film is deoxidized. We used spectroscopic and theoretical methods to analysis change of electronic structure. X-ray absorption spectroscopy (XAS) for O K1-edge and Density Functional Theory (DFT) calculation using VASP code were performed to verify the electronic structure of the film. Also, high resolution x-ray photoelectron spectroscopy (HRXPS) for Ce 3d was carried out to confirm chemical bond of cerium doped $ZrO_2$. Through the investigation of the electronic structure, we verified as followings. (1) During reduction process, binding energy of oxygen is increase. Simultaneously, oxidation state of cerium was change to 4+ to 3+. (2) Cerium 4+ and cerium 3+ states were generated at different energy level. (3) Absorption states in O K edge were mainly originated by Ce 4+ $f_0$ and Ce 3+, while occupied states in valance band were mainly originated from Ce 4+ $f_2$.

• Korean Chemical Engineering Research
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• 제55권5호
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• pp.704-710
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• 2017

가스 하이드레이트 형성원리를 이용한 해수담수화는 이미 상용화된 역삼투 방식에 비하여 아직 실증화 단계이지만 그 공정이 비교적 단순하고 특히 냉매를 객체가스로 사용할 경우 아주 낮은 공정 온도가 필요하지 않아 에너지 소비량(thermal budget)이 향상될 가능성이 있기 때문에 여전히 많은 관심을 받고 있다. 따라서 본 연구에서는 수소불화탄소(HFC, hydrofluorocarbon) 및 수소염화불화탄소(HCFC, hydrochlorofluorocarbon) 계열의 냉매들을 객체가스로 한 가스 하이드레이트 형성 거동을 에너지적인 관점에서 해석하고자 하였고 이를 위해 밀도 범함수(DFT, density functional method) 이론을 기반으로 한 분자모델링을 도입하였다. 객체가스(guest gas)로 R-134a, R-227ea, R-236fa, R-141b를 선정하였으며 계산을 위하여 물 분자로 이루어진 $5^{12}$, $5^{12}6^2$, $5^{12}6^4$의 세가지 구조의 동공들(cavities)을 구성하였다. 동공, 객체가스, 그리고 객체가스가 삽입된 동공의 구조를 분자모델링을 이용하여 각각 최적화하였고 계산된 각 구조의 에너지로부터 동공과 객체가스의 결합에너지(binding energy)를 계산하였다. 마지막으로 결합에너지를 비교함으로써 어느 냉매가 가장 유리한 조건에서 가스하이드레이트를 형성할 지를 판단하였다. 결과적으로 R-236fa가 가장 자발적(spontaneous)으로 가스 하이드레이트를 형성할 것으로 예상되었고 사람에 대한 낮은 독성과 물에 대한 작은 용해도 측면에서도 가장 적절한 선택으로 평가되었다.

• 한국진공학회지
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• 제18권1호
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• pp.9-14
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• 2009

본 연구는 정방정계-$HfO_2$/Si 초격자의 계면 층 구조를 범밀도함수론 (density functional theory)을 이용하여 계산하였다. 입방정계-$HfO_2$는 Si 기판과 에피택시 접합을 위하여 a와 b축의 길이가 증가되면 c축의 길이가 2% 감소하여 정방정계 구조가 되었다. 정방정계-$HfO_2$와 Si 기판의 말단층에 따라서 8 개의 계면 층 모델이 생성되었다. 정방정계-$HfO_2$ (004)$_{1/4}$/Si $(004)_{3/4}$ 초격자구조가 에너지 관점에서 가장 안정하였고, 정방정계-$HfO_2$ $(004)_{1/4}$/Si (002) 초격자구조는 가장 불안정하였다. 에너지 관점에서 가장 불안정한 구조의 경우, 정방정계-$HfO_2$의 계면에 존재하는 2 개의 산소 원자가 Si 기판으로 이동하여 정방정계-$HfO_2$ 초격자구조에 2 개의 산소 공공이 생성되었다.

• 전기화학회지
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• 제16권3호
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• pp.169-176
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• 2013

현재 이차전지에서 사용중인 양극활물질은 구조 안정성이 높은 층상구조(Layered Structure)의 리튬 금속 산화물(Solid State Lithium Oxide Compounds)이 주로 사용된다. 최근에는 리튬이차전지의 성능향상을 위해서 음극활물질과 전해질 사이의 계면뿐만 아니라, 양극활물질과 전해질 사이의 계면에 관한 연구가 활발히 진행되고 있으며, 이러한 계면의 연구를 위해서는 음극활물질 뿐만 아니라, 양극활물질의 표면에 관한 연구도 선행적으로 이루어져야 하는 상황이다. 대표적인 리튬금속 산화물질인 니켈산리튬($LiNiO_2$)과 코발트산리튬($LiCoO_2$)은 서로 매우 유사한 구조를 갖는 층상구조의 양극활물질이다. 코발트산리튬이 다양한 실험적, 이론적 연구가 진행된 반면에, 니켈산 리튬은 실험적 연구에 비해서 이론적 연구가 부족하다. 따라서, 본 연구에서는 니켈산리튬의 X-선 회절계 측정 결과(XRD data)에 나오는9개의 표면 방향을 범밀도함수이론(Density Functional Theory)을 이용하여 니켈산리튬 표면의 표면 에너지를 계산하였다. 니켈산리튬의 X-선 회절계 측정 결과(XRD data)에서는 (003), (104), (101), (110) 결정 등등이 순차적으로 주요하게 존재하는 것으로 확인되었다. 그러나 시뮬레이션을 이용한 각각의 표면 에너지 계산 결과, X-선 회절계 측정 결과와 다른 순서로 안정한 표면 에너지가 나타나는 결과를 얻었다. 따라서 에너지적으로 안정한 표면이자, X-선 회절계에서 주요하게 나타나는 (104)와 (101) 방향의 니켈산리튬 표면이 많이 노출되어 Li 이온의 충방전시 리튬의 삽입 탈리에 영향을 줄 것으로 예상된다.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1697-1702
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• 2014

A novel complex [$Zn(phen)(o-AB)_2$] [phen: 1,10-phenanthroline o-AB: o-aminobenzoic acid] was synthesized and characterized by elemental analysis and X-ray diffraction single-crystal analysis. The crystal crystallizes in monoclinic, space group P2(1)/c with $a=7.6397(6){\AA}$, $b=16.8761(18){\AA}$, $c=17.7713(19){\AA}$, ${\alpha}=90^{\circ}$, ${\beta}=98.9570(10)^{\circ}$, ${\gamma}=90^{\circ}$, $V=2.2633(4)nm^3$, Z = 4, F(000) = 1064, S = 1.058, $Dc=1.520g{\cdot}cm^{-3}$, $R_1=0.0412$, $wR_2=0.0948$, ${\mu}=1.128mm^{-1}$. The Zn(II) is six coordinated by two nitrogen and four oxygen atoms from the 1,10-phenanthroline and o-aminobenzoic acid to furnish a distorted octahedron geometry. The complex exhibits intense fluorescence at room temperature. Theoretical studies of the title complex were carried out by density functional theory (DFT) B3LYP method. CCDC: 898291.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.212-212
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• 2012

The Coverage dependent attachment of multifunctional groups included in threonine molecules adsorbed to Ge (100)$-2{\times}1$ surface was investigated using core-level photoemission spectroscopy (CLPES) and density functional theory (DFT) calculations. The core-level spectra at a low coverage indicated that the both carboxyl and amine groups participated in the bonding with the Ge (100) surface by "O-H dissociated and N-dative bonded structure". However, at high coverage level, additional adsorption geometry of "O-H dissociation bonded structure" appeared possibly to minimize the steric hindrance between adsorbed molecules. Moreover, the C 1s, N 1s, and O 1s core level spectra confirmed that the carboxyl oxygen is more competitive against the hydroxymethyl oxygen in the adsorption reaction. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. Conclusively, we investigate in threonine on Ge (100) surface system that the "O-H dissociated-N dative bonded structure" and the "O-H dissociation bonded structure" are preferred at low coverage and high coverage.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1323-1328
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• 2014

Molecular structures of the various conformational stereoisomers of 2,8,14,20-cyanophenyl pyrogallol[4]arenes 1 were optimized using the mPW1PW91 (hybrid Hartree-Fock density functional) calculation method. The total electronic and Gibbs free energies and the normal vibrational frequencies of the different structures from three major conformations (CHAIR, TABLE, and 1,2-Alternate) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), and 1(rtct)] were analyzed. The mPW1PW91/6-31G(d,p) calculations suggested that $1(rcct)_{1,2-A}$, 1(rctt)CHAIR, and $1(rtct)_{CHAIR}$ were the more stable conformations of the respective stereoisomers. Hydrogen bonding is the primary factor for the relative stabilities of the various conformational isomers, and maximizing the ${\pi}-{\pi}$ interaction between the cyanophenyl rings is the secondary factor. The calculated IR spectra of the more stable conformers [$1(rctt)_{CHAIR}$, $1(rcct)_{1,2-A}$, $1(rtct)_{CHAIR}$] were compared with the experimental IR spectrum of $1(rtct)_{CHAIR}$.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.145.1-145.1
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• 2016

Binding and unbinding between molecular oxygen and metallo-porphyrin is a key process for oxygen delivery in respiration. It can be also used to control spin state of magnetic metallo-porphyrin molecules. Controlling and sensing spin states of magnetic molecules in such reactions at the single molecule level is essential for spintronic molecular device applications. Here, we demonstrate that spin states of metallo-porphyrin on surfaces can be controlled over by binding and unbinding of oxygen molecule, and be sensed using scanning tunneling microscopy and spectroscopy. Kondo localized state of metallo-porphyrin showed significant modification by the binding of oxygen molecule, implying that the spin state was changed. Our density functional theory calculation results explain the observations with the hybridization of unpaired spins in d and ${\pi}^*$ orbitals of metallo-porphyrin and oxygen, respectively. Our study opens up ways to control molecular spin state and Kondo effect by means of molecular binding and unbinding reactions on surfaces.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1873-1878
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• 2011

Under solvent-free conditions and in one-pot, a series of 2-amino-4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-pyridines and 4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-2(1H)-pyridinones were prepared using 3,4-dimethoxyacetophenone, an aldehyde, malononitrile (or ethyl cyanoacetate), and ammonium acetate in the presence of 3-methyl-1-(4-sulfonylbutyl)imidazolium hydrogen sulfate $[HO_3S(CH_2)_4MIM][HSO_4]$ (a Br${\o}$nsted acidic ionic liquid) as the catalyst in very short reaction time. The preference for the formation of more stable tautomers was consistence with the theoretical calculation using the Gaussian 03 program at the B3LYP hybrid density functional level.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1187-1194
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• 2011

The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from c-$CF_3CH_2CHO$. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.