• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1493-1500
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• 1999

The electronic transitions from the ground state to low-lying excited states of CF₃OH have been investigated using high level ab initio quantum mechanical techniques. Also the possible photodissociation procedures of CF₃OH have been considered. The highest level employed in this study is TZP CCSD(T) level of theory. The possible four low-lying excited states can result by the excitation of the lone pair electron (n) in oxygen to σ$^*$ molecular orbital in C-O or O-H bond. The vertical transition (n → σ$^*$) energy is predicted to be 220.5 kcal/mol (130 nm) at TZ2P CISD level to theory. The bond dissociation energies of CF₃OH to CF₃O +H and CF₃+OH have been predicted to be 119.5 kcal/mol and 114.1 kcal/mol, respectively, at TZP CCSD level of theory. In addition, the transition state for the unimolecular decomposition of CF₃OH into CF₂O + HF has been examined. The activation energy and energy separation for this decomposition have been computed to be 43.6kcal/mol and 5.0 kcal/mol including zero-point vibrational energy corrections at TZP CCSD(T) level of theory.ed phenols were also estimated.

• 융합경영연구
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• 제12권4호
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• pp.27-36
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• 2024

Purpose: The paper analyzes for detecting unexpected shocks such as global financial crisis and COVID-19 pandemic, and contagion between countries by capturing in the mean-shift, variance-covariance-shift, and skewness-coskewness-shift parameters of interest rates. Research design, data and methodology: A flexible multivariate model of interest rates is provided by allowing for regime switching and a joint skewed normal distribution. The model is applying to the structural breaks of crisis and contagion between the US and the selected global bond markets during the global financial crisis and COVID-19 pandemic, respectively. Inspection of the moment statistics weakly suggests a flight to safety to the US during the global financial crisis and to Canada during the COVID-19 pandemic. Results: The results indicate that risk averse investors had a higher risk appetite for the US and Canada assets during the crisis regimes, compared to their counterparts. Conclusions: The results show that coskewness contagion dominates correlation contagion, and coskewness contagion is significant for the Korea and Japan-US pairs for the global financial crisis and the Euro-US pair for the COVID-19 pandemic. All channels of structural breaks of crisis and contagion are significant when considered jointly, reinforcing the need to consider contagion and structural breaks during crises in a multivariate setting.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.186-186
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• 2011

[100] 방향으로 4$^{\circ}$ 기울어진 Si(001)-2${\times}$1(vicinal surface)을 초고진공하(UHV)에서 청결하게 하고 열처리하면 rebonded-atom을 가진 DB double step과 이 step에 나란한 아홉 개의 dimer를 가진 평균 폭이 4.0 nm인 single-domain의 (001)-2${\times}$1 테라스의 면으로 재구조된다 [그림 a]. 본 연구에서는 이 표면 위에 Sb을 상온에서 증착하여 덮고 후열처리하면(2 ML, 500$^{\circ}C$ 10 분), Sb-dimer가 Si 표면을 한 층 덮고 (001) 테라스의 Sb-dimer 방향이 DA double-step과 수직을 이루는 1${\times}$2 구조를 이룬다는 사실을 STM으로 확인하였다 [그림 b]. 이러한 Sb-passivation의 효과는 표면 Si-dimer의 부분적으로 채워진 dangling-bond를 Sb-dimer의 완전히 채워진 고립쌍(lone-pair)으로 바꿈으로써 표면 자유 에너지를 줄이고, 나아가 계면 Si 층은 bulk에 유사하게 되는 데에 있다. 이 passivation 된 표면은 Ge/Si 등의 heteroepitaxy에 사용할 수 있고, 특히 single-domain을 유지하며 step 방향에 대해 평행인 dimer-row로 이루어져 있어서 원자나 전자의 이동에 비등방적 효과를 증가시킬 것이 예측된다.

• Bulletin of the Korean Chemical Society
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• 제33권1호
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• pp.153-158
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• 2012

The hydrogenation of $AlB_2$-type BaGaGe exhibits a metal to insulator (MI) transition, inducing a puckering distortion of the original hexagonal [GaGe] layers. We investigate the electronic structure changes associated with the hydrogen-induced MI transition, using extended H$\ddot{u}$ckel tight-binding band calculations. The results indicate that hydrogen incorporation in the precursor BaGaGe is characterized by an antibonding interaction of $\pi$ on GaGe with hydrogen 1s and the second-order mixing of the singly occupied antibonding $\pi^*$ orbital into it, through Ga-H bond formation. As a result, the fully occupied bonding $\pi$ band in BaGaGe changes to a weakly dispersive band with Ge pz (lone pair) character in the hydride, which becomes located just below the Fermi level. The Ga-Ge bonds within a layered polyanion are slightly weakened by hydrogen incorporation. A rationale for this is given.

• Bulletin of the Korean Chemical Society
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• 제12권1호
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• pp.17-22
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• 1991

Fourier transform infrared spectroscopy has been applied to the characterization of titania supported molybdena. The equilibrium adsorption method seemed to produce molybdena species homogeneously dispersed on the support. Even under an oxidizing environment, molybdena species appeared to be able to possess coordinatively unsaturated $Mo^{5+}$ ions owing to the natures of TiO$_2$, i.e. oxygen deficiency and permeability toward oxygen diffusion. At the initial stage of reduction, the terminal double bond oxygen ( Mo=O ) seemed to be removed, generating presumably $Mo^{4+}$. The carbonyl bands at 2198 and 2190 $cm^{-1}$ observed after CO exposure were attributed to the $Mo^{5+}{\cdots}CO\;and\;Mo^{4+}\;{\cdots}CO$ complexes, respectively, while the band pair at 2136 and 2076 $cm^{-1}$ to $Mo^{4+}(CO)_2$.

• 대한화학회지
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• 제26권2호
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• pp.65-72
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• 1982

여러 형태의(n${\pi}$/m) 및 (n-${\sigma}^*$) 구조가 에너지에 미치는 구조적인 기여를 살펴보기 위하여 n-프로필아민, n-프로필아민 라디칼, trans-및 cis-에틸렌 디아민에 대한 STO-3G 수준의 계산을 수행하였다. 그 결과 (5${\pi}$/5)구조가 (4${\pi}$/4)구조는 각각 인력 및 반발의 비결합 상호작용을 나타내었으며 서로 부가관계를 가짐을 알았다. anti(n-${\sigma}^*$) 구조는 syn(n-${\sigma}^*$)구조보다 강한 hyperconjugation효과를 보이지만 anti(n-${\sigma}^*$)구조에서 강한 핵간 반발력을 가지기 때문에 결과적으로 불안정한 겉보기 효과를 나타내었다. 더우기 안정화${\pi}$ -비결합 (5${\pi}$/5)구조는 anti(${\pi}$-${\sigma}^*$)구조를, 불안정화 ${\pi}$-비결합(4${\pi}$/4)구조는 syn(n-${\sigma}^*$)구조를 수반하며 상호 보강적으로 작용함을 알았다. 또한 이러한 상호 보강성이 일반적인 성질임을 알았다. 끝으로 말단의 고립 전자쌍에 의한 through-bond 상호작용을 논의하였으며 이러한 상호작용으로 에너지 준위가 $n_+ = \frac{1}{\sqrt{2}}(n_1\;+\;n_2)$와 $n_-\;=\;\frac{1}{\sqrt{2}}(n_1\;-\;n_2)$로 갈라지는데 이때 고립 전자쌍의 간단한 overlap pattern으로 n_준위가 안정한 준위임을 알았다.

• 한국재료학회지
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• 제10권10호
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• pp.665-670
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• 2000

실온에서 직접 접합된 실리콘 기판의 접합강도를 향상기키기 위하여 기존의 고온 로내 열처리법을 대체할 수 있는 선형 열처리법을 개발하였다. 한 개의 열원과 타원형 반사경으로 구성된 선형 열처리법은 접합면의 간격이 열처리 온도의 증가와 더불어 감소하는 특성과 온도 증가와 더불어 접합면에 생성된는 기체상의 밀도가 증가하는 현상을 응용하여 접합면의 기체상을 밀도차이를 이용하여 기판 외부로 방출시키는 방법으로 Si$\mid$$\mid$Si 기판쌍 및 Si$\mid$$\mid$$SiO_2/Si$ 기판쌍의 직접 접합에 적용하여 보았다. IR camera와 HRTEM으로 직접 관찰한 접합면은 실온에서 접합면에 침투한 외부 불순물에 의한 비접합 영역을 제외하고는 자제 생성된 기체상에 의한 비접합 영역은 나타나지 않았고 매우 깨끗한 접합계면을 나타내었다. 접합된 기판쌍을 Crack opening법과 인장시험법을 적용하여 접합 강도를 측정하였다. 접합 강도는 열처리 온도의 증가와 더불어 점차로 증가하였고 두 측정방법 모두 동일한 경향성을 나타내었다.

• 대한임상검사과학회지
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• 제36권2호
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• pp.115-120
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• 2004

혼합 amino acid의 선택적 분리를 위해 bulk liquid membrane system을 이용하였으며, p-diamethylaminobenzaldehyde(DAB), sulfosalicylic acid (SSA), 1-naphtol이 amino acid의 선택적 분리를 위한 효과적인 carrier로 사용될 수 있음을 확인하였다. 그 결과 sulfosalicylicacid에 대해서 Ala에 대한 선택성을 관찰할 수 있었으며, 1-naphtol에 대해서는 염기성 상태에서 Leu을 약산성 및 중성상태에서는 Val을 선택적으로 분리할 수 있었다. DAB에 대해서는 강산성에서 Phe을, 강알카리 조건에서 Ile를 선택적으로 분리할 수 있었다. Separation mechanism은 SSA와 1-naphtol의 경우에는 ion pair mechanism으로, DAB의 경우에는 imine 결합의 생성반응으로 설명할 수 있었다. 따라서, Liquid membrane을 이용한 생체시료 내의 아미노산을 선택적으로 분리함에 유용성이 클 것으로 사료된다.

• Bulletin of the Korean Chemical Society
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• 제31권6호
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• pp.1704-1710
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• 2010

The structure of a 2D grid-like copper(II) complex [Cu$(NCO)_2$(pyz)](pyz=pyrazine) (1) consists of 1D chains of Cu-pyz units connected by double end-on (EO) cyanato bridges. Each Cu(II) ion has a distorted octahedral coordination, completed by the four EO cyanato and two pyrazine ligands. Magnetic interactions through EO cyanato and pyrazine bridges in 1 are discussed on the basis of DFT broken-symmetry calculations at the B3LYP level. For model dicopper(II) complexes I (bridged by cyanato) and II (bridged by pyrazine), electronic structure calculations reproduce very well the experimental couplings for the S = 1/2 ferromagnetic and antiferromagnetic exchange-coupled 2D system: the calculated exchange parameters J are +1.25 $cm^{-1}$ and -3.07 $cm^{-1}$ for I and II, respectively. The $\sigma$ orbital interactions between the Cu $x^2-y^2$ magnetic orbitals and the nitrogen lone-pair orbitals of pyrazine are analyzed from the viewpoint of through-bond interaction. The energy splitting of 0.106 eV between two SOMOs indicates that the superexchange interaction should be antiferromagnetic in II. On the other hand, there are no bridging orbitals that efficiently connect the two copper(II) magnetic orbitals in I because the HOMOs of the basal-apical NCO bridge do not play a role in the formation of overlap interaction pathway. The energy separation in the pair of SOMOs of I is calculated to be very small (0.054 eV). This result is consistent with the occurrence of weakly ferromagnetic properties in I.