• Bulletin of the Korean Chemical Society
• /
• 제23권2호
• /
• pp.215-220
• /
• 2002

The structures of 1-fluorosilatrane and the silatranyl cation were calculated by Hartree-Fock (HF), Mofller-Plesset second order (MP2), and various density functional theory (DFT) methods using many different basis sets, demonstrating that the Si-N bonds in two species are quite different. The N${\rightarrow}$Si bond distance of 1-fluorosilatrane from the hybrid DFT calculations $({\sim}2.32{\AA})$ using the Perdew-Wang correlation functional agrees with the gas phase experimental value $(2.324{\AA})$, while other functionals yield larger distances. The MP2 bond distance (2.287${\AA}$ with 6-311$G^{\ast}$) is shorter, and the HF one (2.544 ${\AA}$ with 6-311$G^{\ast}$) larger than those of DFT calculations. The MP2 bond distance is in good agreement with experiment indicating that the electron correlations are crucial for the correct description of the N${\rightarrow}$Si interaction. The silatranyl cation is a stable local minimum on the potential energy surface in all methods employed suggesting that the cation could be a reaction intermediate. The Si-N bond length for the cation is about 1.87 ${\AA}$ for all calculations tested implying that the Si-N bond is mainly conventional. Bonding characteristics of the Si-N bond in two species derived from the natural bond orbital analysis support the above argument based on calculated bond lengths.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
• /
• pp.415.1-415.1
• /
• 2014

Carrying out first-principles calculations, we study N-doped capped carbon nanotube (CNT) electrodes applied to DNA sequencing. While we obtain for the face-on nucleobase junction configurations a conventional conductance ordering where the largest signal results from guanine according to its high highest occupied molecular orbital (HOMO) level, we extract for the edge-on counterparts a distinct conductance ordering where the low-HOMO thymine provides the largest signal. The edge-on mode is shown to operate based on a novel molecular sensing mechanism that reflects the chemical connectivity between N-doped CNT caps that can act both as electron donors and electron acceptors and DNA functional groups that include the hyperconjugated thymine methyl group[1].

• Bulletin of the Korean Chemical Society
• /
• 제23권2호
• /
• pp.221-224
• /
• 2002

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to ethyl-${\alpha}$-cyanocinnamates (ECC;$YC_6H_4CH$=C(CN)COOEt) have been investigated in acetonitrile at $30.0^{\circ}C$. The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of ${\sigma}^-$ or $R^-$ for the activating groups (CN and COOEt). Natural. bond orbital ${\pi}^{\ast}_{c=c}$ calculations show that the contribution of COOEt group may not be fully effective despite the coplanar molecular structure. The selectivity parameters including the cross-interaction constant (${\rho}_{xy}$ = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects ($k_H/k_D$=2.5-2.8) involving deuterated BA ($XC_6H_4CH_2ND_2$) nucleophiles and activation parameters (${\Delta}H^{\neq}=4{\sim}6\;kcal\;mol^{-1};{\Delta}S^{\neq}=-45{\sim}-52\;e.u.$) suggest a cyclic transition state in which N-$C_{\alpha}$ and H-$C_{\beta}$ bonds are formed concurrently.

• 한국재료학회지
• /
• 제17권12호
• /
• pp.637-641
• /
• 2007

The total energy and strength of Mg alloy doped with Al, Ca and Zn, were calculated using the density functional theory. The calculations was performed by two programs; the discrete variational $X{\alpha}\;(DV-X{\alpha})$ method, which is a sort of molecular orbital full potential method; Vienna Ab-initio Simulation Package (VASP), which is a sort of pseudo potential method. The fundamental mixed orbital structure in each energy level near the Fermi level was investigated with simple model using $DV-X{\alpha}$. The optimized crystal structures calculated by VASP were compared to the measured structure. The density of state and the energy levels of dopant elements was discussed in association with properties. When the lattice parameter obtained from this study was compared, it was slightly different from the theoretical value but it was similar to Mk, and we obtained the reliability of data. A parameter Mk obtained by the $DV-X{\alpha}$ method was proportional to electronegativity and inversely proportional to ionic radii. We can predict the mechanical properties because $\Delta{\overline{Mk}}$is proportional to hardness.

• 한국자기학회지
• /
• 제26권4호
• /
• pp.119-123
• /
• 2016

Cu 원자 4개를 포함한 cubane 구조의 분자자성체의 전기구조 및 자기적 성질을 제1원리의 범밀도함수법을 이용하여 계산하였다. 계산 된 결과, Cu 원자는 +2가를 가지며, 팔면체 배위자중 면내 짧은 4개의 배위산소원자로 인해 3d $x^2-y^2$ hole 궤도를 가지고 있었다. 스핀배열에 따른 총 에너지 계산에서 면내는 반강자성, 면간은 강자성 자기구조가 가장 안정되었다. 교환상호작용 J의 크기는 면내의 J가 훨씬 크고 반강자성 성질을 나타내었으며, 나머지 면간의 J값은 아주 작았다. 이러한 원인은 Cu $x^2-y^2$ hole 궤도정렬로 인하여 면내 강한 초교환상호작용의 결과이다.

• 대한화학회지
• /
• 제38권1호
• /
• pp.55-60
• /
• 1994

유기규소 중합반응에서 나타나는 중간체 $Cp_2TiSiHPh(1),\;[Cp_2Ti]_2[{\mu}-HSi(HPh)][{\mu}-H]$ (2) 그리고 $[Cp_2TiSiH_2Ph]_2$ (3)화합물들의 전자구조를 EHT방법으로 연구하였다. 1 화합물의 안정한 구조는 Cs로 변형된 형태이고 $SiH_2$의 회전에너지는 약 14 kcal/mol로 나타났다. 전자결핍분자인 2와 3 화합물의 결합특성을 전자구조를 통하여 규명하였다. 또한 Ti금속이 Si-H의 $\sigma$ 결합과 작용할 가능성을 설명하였다.

• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.1
• /
• pp.259-262
• /
• 2003

The surface electronic state of rutile $TiO_2$, which is an oxide semiconductor and has a wide band gap of 3.1 $\sim$ 3.5 eV, was calculated by DV-$X_{\alpha}$ method, which is a sort of the first principle molecular orbital method and uses Hartre-Fock-Slater approximation. The $[Ti_{15}O_{56}]^{-52}$ cluster model was used for the calculation of bulk state and the $[OTi_{11}O_{34}]^{-24}$ model for the surface state calculation. After calculations, the energy level diagrams and the deformation electron density distribution map were compared in both models. As results, it was identified that the surface energy levels are found between the valence and conduction band of bulk $TiO_2$ on the surface area. The energy values of these surface-induced levels are lower than conduction band of bulk $TiO_2$ by 0.1 $\sim$ 1 eV. From this fact, it is expected that the surface energy levels act as donar levels in n-type semiconductor.

• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 2004년도 하계학술대회 논문집 Vol.5 No.1
• /
• pp.309-312
• /
• 2004

The electronic structure of ZnO oxide semiconductor having high optical transparency and good electric conductivity was theoretically investigated by $DV-X_{\alpha}$(the discrete variation $X_{\alpha}$) method, which is a sort of the first principle molecular orbital method using Hatre-Fock-Slater approximation. The electrical and optical properties of ZnO are seriously affected by the addition of impurities. The imnurities are added to ZnO in order to increase the electric conductivity of an electrode without losing optical transparency. In this study, the effect of impurities of III and IV family on the band structure, impurity levels and the density of state of ZnO were investigated. The cluster model used for calculations was $[MZn_{50}O_{53}]^{-2}$(M=elements belonging to III and IV family).

• 대한화학회지
• /
• 제33권6호
• /
• pp.571-576
• /
• 1989

$[M(NH_3)_5Cl]^{2+}$착물에 대하여 상대론적으로 파라미터화된 확장 Huckel(REX) 계산을 수행하였다. 궤도함수 및 overlap population에 대한 계산 결과는 실험적인 자료와 일치하였다. 또한 전자구조에 대하여 상대성 효과를 감안한 REX와 비상대론적인 EHT의 계산 결과를 서로 비교하였다. 이들 착화합물의 M-Cl 결합에 대한 파이 결합성은 $d^6$계 착물에서 보다 $d^3$ 및 $d^5$계 착물의 경우가 더 중요함을 알 수 있었다.

• 대한화학회지
• /
• 제53권3호
• /
• pp.266-271
• /
• 2009

고체 화합물 La7Os4C9 속에 있는 [Os4C9]21‑ 사슬의 전자구조와 화학결합을 extended Hückel 계산 결과에 의해서 논의하였다. 탄소 원자는 물론 (C2)2‑ 분자의 결합 특성은 비교적 큰 Os-C 상호작용을 나 타내었고 특히 (C2)2‑ 분자의 결합길이 증가는 Fermi level 바로 아래에 Os-C2(1 πg) 결합 밴드의 존재로 인 해서 반결합 1πg 오비탈에 부분적인 전자점유가 일어나기 때문인 것으로 해석된다.