• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.215-220
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• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.415.1-415.1
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• 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
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• v.23 no.2
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• pp.221-224
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• 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.

• Korean Journal of Materials Research
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• v.17 no.12
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• pp.637-641
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• 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.

• Journal of the Korean Magnetics Society
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• v.26 no.4
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• pp.119-123
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• 2016

We have studied electronic and magnetic structure of cubane-type Cu magnetic molecule using density functional method. The calculated density of states show that Cu has 3d $x^2-y^2$ hole orbital because of short distances between Cu atom and in-plane 4 ligand atoms. The calculated total energy with in-plane antiferromagnetic spin configuration is lower than those of ferromagnetic configurations. The calculated exchange interaction J between in-plane Cu atoms is much larger than those between out-plane Cu atoms, since the $x^2-y^2$ hole orbital ordering of Cu 3d orbitals induces strong super-exchange interaction between in-plane Cu atoms.

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.55-60
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• 1994

Molecular orbital calculations at the extended Huckel level have been carried out for $Cp_2TiSiHPh(1),\;[Cp_2Ti]_2[{\mu}-HSi(HPh)][{\mu}-H] (2),\;and\;[Cp_2TiSiH_2Ph]_2$ (3) complexes which are important intermediates in organosilane polymerization. Stable geometry of complex 1 is not $C_{2V}$, but Cs symmetry and the rotational energy barrier of $SiH_2$ unit is computed to be 14 kcal/mol. The orbital interaction diagrams are studied to characterize the chemical bonding for the electron deficient systems, 2 and 3. It is possible for Si-H to be coordinated to the Ti metal using $\sigma$ bonding.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.259-262
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• 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.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.07a
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• pp.309-312
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• 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).

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.571-576
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• 1989

The relativistically parameterized Extended Huckel (REX) calculations are carried out for $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir). The calculated orbital and overlap populations agree with experimental data. The REX calculations on the electronic structure have been also compared with nonrelativistic EHT results. A ${\phi}$-bonding in M-Cl bond is founded to be more important for the $d^3$, $d^5$complexes than the $d^6$ system.

• Journal of the Korean Chemical Society
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• v.53 no.3
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• pp.266-271
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• 2009

In the recently synthesized rare earth transition metal carbide $La_7O_{s4}C_9$ one finds one-dimensional organometallic $[O_{s4}C_9]^{21-}$ polymers embedded in a $La^{3+}$ ionic matrix. The electronic structure of the polymeric $[O_{s4}C_9]^{21-}$ chain was investigated by density of states (DOS) and crystal orbital overlap population (COOP), using the extended Huckel algorithm. A fragment molecular orbital analysis is used to study the bonding characteristics of the $C_2$ units in $La_7O_{s4}C_9$ containing $C_2$ units and single C atoms as well. The title compound contains partially filled Os and carbon bands leading to metallic conductivity. As the observed distances already indicated, the calculations show extensive Os-C interactions. The C-C bond distance in the diatomic $C_2$ units ($d_{C-C}$=131 pm) in the solid is significantly increased relative to $${C_2}^{2-}$$ or acetylene, because antibonding $1{\pi}_g$ orbitals are partially filled by the Os-$C_2(1\;{\pi}_g)$ bonding contribution found at and below the Fermi level.