• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3690-3694
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• 2013

The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

• 대한화학회지
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• 제54권3호
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• pp.275-282
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• 2010

분자 내 수소결합 가능성을 가지고 있는 2-fluorocyclopropanemethanol과 2-chlorocyclopropanemethanol에 대하여 MP2/6-311++G(d,p) 방법과 B3LYP/6-311++G(d,p) 방법으로 최적화 계산을 수행하였다. 두 분자 모두 가장 안정한 conformer에서 O-H의 수소가 F나 Cl을 향하고 있어 수소결합 가능성을 보이기는 하나 $H{\cdots}F$, $H{\cdots}Cl$ 거리가 van der Waals radii보다 커서 강한 수소결합이라 보기 힘들고 두 번째 안정한 conformer의 경우가 가까운 $H{\cdots}F$, $H{\cdots}Cl$ 거리를 보이며 더 강한 수소결합 가능성을 보였다. 그러나 에너지가 5 ~ 7 kJ 더 높게 나타났다. Methanol group과 F나 Cl이 서로 반대 방향을 향할 때 일반적으로 안정하나 앞의 가장 안정한 conformer보다는 에너지가 높다.

• 한국중재학회지:중재연구
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• 제30권1호
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• pp.39-66
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• 2020

Under the doctrine of separability, if the party did not specifically challenge the validity of the arbitration clause, then it is presumed valid, and arbitrators would still have authority to adjudicate disputes within the scope of the arbitration clause. Further, the Primerica and Spahr decisions address whether a court or an arbitrator should adjudicate a claim that a contract containing an arbitration clause is void ab initio due to mental incapacity. If the arbitration agreement is separable, as was found in Primerica, then the "making" of the agreement is not at issue when the challenge is directed at the entire contract and arbitrators may exercise authority. If an arbitration provision is not separable from the underlying contract, as in Spahr, a defense of mental incapacity necessarily goes against both the entire contract and the arbitration agreement, so the "making" of the agreement to arbitrate is at issue, and the claim is for courts to decide. Although no bright line rule can be established to deal with challenges of lack of mental capacity to an arbitration agreement, the rule in Prima Paint should not be extended to this defense. Extending the rule in Prima Paint would force an individual with a mental incapacity to elect between challenging the entire contract and challenging arbitration. Accordingly, there should be a special set of rules outside of the context of Prima Paint to address the situation of status-based defenses, specifically mental capacity defenses, to contracts containing arbitration provisions.

• Bulletin of the Korean Chemical Society
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• 제32권2호
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• pp.510-514
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• 2011

Photodissociation dynamics of allyl alcohol ($H_2C$=CH-$CH_2OH$) has been investigated at 205 - 213 nm along the UV absorption band by measuring rotationally-resolved laser-induced fluorescence spectra of OH radicals. Observed energy partitioning of the available energy among products at all photon energies investigated was similar and the barrier energy for OH production is about 574.7 kJ/mol from the OH yield measurements. The potential energy surfaces for the $S_0$, $T_1$, and $S_1$ excited states along the dissociation coordinate were obtained by ab initio quantum chemical calculations. The observed energy partitioning was successfully modeled by the "barrier-impulsive model" with the reverse barrier and the geometry obtained by the calculated potential energy surfaces. The dissociation takes place on the $T_1$ excited state potential energy surface with an energy barrier in the exit channel and a large portion of the photon energy is distributed in the internal degrees of freedom of the polyatomic products.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.185.2-185.2
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• 2014

We have studied the atomic and electronic structure of graphene nanoribbons (GNRs) on a hexagonal boron nitride (h-BN) sheet with intercalated atoms using first-principles calculations. The h-BN sheet is an insulator with the band gap about 6 eV and then it may a good candidate as a supporting dielectric substrate for graphene-based nanodevices. Especially, the h-BN sheet has the similar bond structure as graphene with a slightly longer lattice constant. For the computation, we use the Vienna ab initio simulation package (VASP). The generalized gradient approximation (GGA) in the form of the PBE-type parameterization is employed. The ions are described via the projector augmented wave potentials, and the cutoff energy for the plane-wave basis is set to 400 eV. To include weak van der Waals (vdW) interactions, we adopt the Grimme's DFT-D2 vdW correction based on a semi-empirical GGA-type theory. Our calculations reveal that the localized states appear at the zigzag edge of the GNR on the h-BN sheet due to the flat band of the zigzag edge at the Fermi level and the localized states rapidly decay into the bulk. The open-edged graphene with a large corrugation allows some space between graphene and h-BN sheet. Therefore, atoms or molecules can be intercalated between them. We have considered various types of atoms for intercalation. The atoms are initially placed at the edge of the GNR or inserted in between GNR and h-BN sheet to find the effect of intercalated atoms on the atomic and electronic structure of graphene. We find that the impurity atoms at the edge of GNR are more stable than in between GNR and h-BN sheet for all cases considered. The nickel atom has the lowest energy difference of ~0.2 eV, which means that it is relatively easy to intercalate the Ni atom in this structure. Finally, the magnetic properties of intercalated atoms between GNR and h-BN sheet are investigated.

• 한국자기학회지
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• 제25권4호
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• pp.101-105
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• 2015

희토류 금속이나 4d/5d 전이금속을 포함하지 않은 3d 전이금속 Fe와 Ni 원소만을 적절하게 배열해도 강한 수직 자기이방성을 가질 수 있음을 예측한 이론 계산 결과가 최근 보고된 바 있다. 그 계산에서는 Fe 층을 표면으로 하는 계만을 고려하였는데 본 논문에서는 Ni가 표면일 때의 자기이방성 에너지를 제일원리계산 방법으로 계산하여 자기이방성을 조절할 수 있는 방안이 있을 수 있는지를 알아 보았다. Fe(001) 표면에 Ni 원소 한 층이 덮였을 때[Ni/Fe(001)]의 자성과 자기이방성을 제일원리계산 방법으로 VASP과 FLAPW 방법을 상호 보완적으로 사용하면서 계산 결과를 비교해 보았다. VASP에 의한 결과는 FLAPW 방법으로 얻은 결과와 큰 차이가 없었고, Fe와 Ni의 강한 띠 혼합으로 Fe와 Ni의 자기모멘트가 모두 증가하였으며 Ni/Fe(001)은 수평 자기이방성을 가지는 것으로 계산되었다. 원자 별 자기이방성 기여도 계산에 의하면 자기이방성에 결정적인 역할을 하는 것은 Ni표면 층임을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제29권3호
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• pp.627-640
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• 2008

The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

• Bulletin of the Korean Chemical Society
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• 제34권4호
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• pp.1232-1236
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• 2013

The Cu cation binding sites of $[Cu(I){\cdot}d(CpG){\cdot}d(CpG)-2H]^{-1}$ complex have been investigated to explain the $[Cu{\cdot}DNA]$ biological activity caused by the Cu association to DNA. The structure of $[Cu(I){\cdot}d(CpG){\cdot}d(CpG)-2H]^{-1}$ complex was investigated by electrospray ionization mass spectrometry (ESI-MS). The fragmentation patterns of $[Cu(I){\cdot}d(CpG){\cdot}d(CpG)-2H]^{-1}$ complex were analyzed by MS/MS spectra. In the MS/MS spectra of $[Cu(I){\cdot}d(CpG){\cdot}d(CpG)-2H]^{-1}$ complex, three fragment ions were observed with the loss of d(CpG), {d(CpG) + Cyt}, and {d(CpG) + Cyt + dR}. The Cu cation binds to d(CpG) mainly by substituting the $H^+$ of phosphate group. Simultaneously, the Cu cation prefers to bind to a guanine base rather than a cytosine base. Five possible geometries were considered in the attempt to optimize the $[Cu(I){\cdot}d(CpG){\cdot}d(CpG)-2H]^{-1}$ complex structure. The ab initio calculations were performed at B3LYP/6-31G(d) level.

• 폴리머
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• 제30권6호
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• pp.453-463
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• 2006

분자 모델에 의한 전산 모사는 단백질 접힘, 미셀화, 블록공중합체의 규칙구조화 등 다양한 고분자 계의 자기조립 현상을 예측하거나 그 조립 메커니즘을 밝히는 데 특별히 유용한 연구방법이다. 자기조립 현상은 분자 수, 분자 크기 등, 계의 속성에 따라 나노미터 이하의 현상으로부터 마이크론이나 그 이상의 길이 스케일의 현상까지 조립 구조의 길이 스케일이 매우 광범위하기 때문에 다양한 계의 모든 조립 현상을 양자역학적 방법과 같은 궁극의 근본원칙에 의해 모사하는 것은 현실적인 시간 내에서 불가능하다. 이러한 문제들을 해결하기 위해 계를 기술하는 과정에서 필요 이상으로 세밀한 표현을 생략하여 모델을 다른 관점에서 재구성하는 방법이 있는데 재구성된 모델은 그 관점에 따라 크게 '원자 수준'의 모델과 '메조 스케일 수준'의 모델로 분류할 수 있다. 본 총론에서는 고분자 자기조립 현상과 관련하여 이 두 가지 관점에 따른 모델과 모사 방법들에 대해 살펴보고자 한다.

• 한국자기학회지
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• 제16권4호
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• pp.193-196
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• 2006

제일원리적 국소 스핀밀도 근사에 의한 계산방법을 이용하여 Ni 나노와이어에 대한 전자구조와 자기적 성질을 연구하였다. 단위 세포당 Ni 원자의 개수(n = 1 − 4)에 따른 구조적 특성에 따라 각각의 나노와이어에 대한 결합에너지와 자기모멘트를 계산하였다. 계산결과 지그재그-사각형 $Ni_4$ 나노와이어가 에너지적으로 가장 안정하였다. 또한 Ni 나노와이어의 자기모멘트는 선형 나노와이어 Ni1가 $1.34 {\mu_B}/atom$ 로 가장 큰 값을 나타냈으며, 단위 세포당 원자 개수가 증가될수록 자기모멘트는 감소하여 사각형 나노와이어 $Ni_4$의 자기모멘트가 $0.91 {\mu_B}/atom$ 로 가장 작은 값을 나타냈다. $Ni_n$(n = 1 − 4)의 각각의 구조들에 대한 상태밀도, 에너지 띠 등의 전자구조 계산결과를 제시하고 논의 검토하였다.