• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1875-1880
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• 2010

A dicycle pyrazoline derivative, 1-phenyl-5-(p-fluorophenyl)-3,4-($\alpha$-p-fluoro-tolylenecyclohexano) pyrazoline, was synthesized and characterized by elemental analysis, IR, UV-vis, fluorescence spectra and X-ray single crystal diffraction. Density function theory (DFT) calculations were performed by using B3LYP method with 6-$311G^{**}$ basis set. The optimized geometry can well simulate the molecular structure. Vibrational frequencies were predicted, assigned and compared with the experimental values, which suggest that B3LYP/6-$311G^{**}$ method can well predict the IR spectra. Both the experimental electronic absorption spectra and the predicted ones by B3LYP/6-$311G^{**}$ method reveal three electron-transition bands, with the theoretical ones having some red shifts compared with the experimental data. Natural bond orbital analyses indicate that the absorption bands are mainly derived from the contribution of n $\rightarrow\pi^*$ and $\pi\rightarrow\pi^*$ transitions. Fluorescence spectra determination shows that the title compound can emit blue-light at about 478 nm. On the basis of vibrational analysis, the thermodynamic properties of title compound at different temperature have been calculated, revealing the correlations between $C^0_{p,m}$, $S^0_m$, $H^0_m$ and temperature.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.15-19
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• 1980

CNDO/2, EHT molecular orbital methods are used to investigate the electronic structure and reactivity of glycinato, glycine ester ligands. The results show that bidentate glycinato has a more stable structure, Gly-I with a $105.9^{\circ}$dihedral angle between ${\Delta}O_4C_3C_2$ and ${\Delta}C_3C_2N_1$ than Gly-Ⅱ. The electron inductive effects in the alkyl group substituted glycine ester ligands can also be derived from the calculation. According to the electron density, qN of ligands on the basis of CNDO/2 MO calculations, it is concluded that the stabilities are in the order of glycinato > Gly-Et-ester > Gly-i-Pr-ester > Gly-Me-ester.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.645-645
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• 2013

Applying a first-principles computational approach combining density-functional theory and matrix Green's function calculations, we have studied the effects [2+2] cycloaddition olligormerization of fullerene $C_{60}$ chains on their junction charge transport properties. Analyzing first the microscopic mechanism of the switching realized in recent scanning tunneling microscope (STM) experiments, we found that, in agreement with experimental conclusions, the device characteristics are not significantly affected by the changes in electronic structure of $C_{60}$ chains. It is further predicted that the switching characteristics will sensitively depend on the STM tip metal species and the associated energy level bending direction in the $C_{60}-STM$ tip vacuum gap. Considering infinite $C_{60}$ chains, however, we confirm that unbound $C_{60}$ chains with strong orbital hybridizations and band formation should in principle induce a much higher conductance state. We demonstrate that a nanoelectromechanical approach in which the $C_{60}-STM$ tip distance is maintained at short distances can achieve a metal-independent and drastically improved switching performance based on the intrinsically better electronic connectivity in the bound $C_{60}$ chains.

• Carbon letters
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• v.28
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• pp.55-59
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• 2018

Transition-metal-embedded carbon nanotubes (CNTs) have been accepted as a novel type of sensing material due to the combined advantage of the transition metal, which possesses good catalytic behavior for gas interaction, and CNTs, with large effective surface areas that present good adsorption ability towards gas molecules. In this work, we simulate the adsorption of $O_2$ and $O_3$ onto Rh-doped CNT in an effort to understand the adsorbing behavior of such a surface. Results indicate that the proposed material presents good adsorbing ability and capacities for these two gases, especially $O_3$ molecules, as a result of the relatively large conductivity changes. The frontier molecular orbital theory reveals that the conductivity of Rh-CNT would undergo a decrease after the adsorption of two such oxidizing gases due to the lower electron activity and density of this media. Our calculations are meaningful as they can supply experimentalists with potential sensing material prospects with which to exploit chemical sensors.

• Journal of the Korean Chemical Society
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• v.41 no.7
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• pp.351-356
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• 1997

Extended Huckel Molecular Orbital (EHMO) calculations of haloallene (1-halo-3-phenyl-1,2-propadiene) derivatives have been performed. From the MO calculation data and kinetic experimental results, the mechanism for the hydrolysis of haloallenes is proposed.; Below pH 8.0, the hydrolysis proceeds through a solvent assisted $S_N1$ mechanism involving the formation of carbonium ion Ⅱ as intermediate. However above pH 9.5, the hydrolysis proceeds through an $S_N2'$ mechanism via transition state Ⅲ.

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.13-20
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• 1994

Substituted anthrasemiquinone radical anions, which were formed by laser flash photoreduction of the substituted anthraquinone (1,4-DHAQ, 1,5-DHAQ, 1,8-DHAQ, 1,8-DCAQ), were studied by the electron spin resonance spectroscopy in the mixed solvents of the 2-propanol and the triethylamine. Hyperfine splitting constants (hfsc) were determined by simulating the ESR spectra. Extended Huckel Molecular Orbital (EHMO) calculations were performed to obtain $\pi$ spin densities for these quinones. The hyperfine splitting constants could be assigned to specific protons on the basis of $\pi$ spin densities.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3211-3217
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• 2013

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of three D-${\pi}$-A-type organic dyes (C1-1, D5 and TH208) containing identical ${\pi}$-spacers and electron acceptors, but different aromatic amine electron-donating groups (tetrahydroquinoline, triphenylamine and phenothiazine). The coplanar geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating ability of tetrahydroquinoline is stronger than those of triphenylamine and phenothiazine. The computed orbital energy levels of these dyes confirm that the electrons could be injected from the excited dyes to the semiconductor conduction band and the oxidized dyes could be reduced effectively by electrolyte. The TD-DFT results show that the CAM-B3LYP/6-31+G(d, p) is suitable for calculating the absorption spectra. The first absorption band for these dyes is assigned to the HOMO${\rightarrow}$LUMO and HOMO-1${\rightarrow}$LUMO transitions.

• Korean Journal of Crystallography
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• v.14 no.1
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• pp.16-23
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• 2003

The electronic structure and chemical bonding of β-MnO₂ were theoretically investigated by DV-X/sub α/ (the discrete variation X/sub α/) method. which is a sort of the first principle molecular orbital method using Hatre-Fock-Slater approximation. The calculations on several cluster models having different sizes were carried out for the determination of a model suited for analyzing bulk state. The Mn/sub 15/O/sub 56/ model was selected as a sufficiently suitable model for the calculation of electronic state and chemical bonding by the comparison of the calculated XPS (X-ray photo-electron spectrum) and experimentally measured XPS. By using this model, the electron energy level, the density of state, the bond overlap population, the charge density distribution, and the net ionic transfer between cations and anions were calculated and discussed.

• Journal of the Korean Chemical Society
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• v.20 no.2
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• pp.111-117
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• 1976

The configuration and conformation of methyl benzamidoxime have been studied from extended Huckel molecular orbital calculations.The results show that the E-configuration of the C=N double bond is favored compared with that of Z-configuration with the sp-conformation of the C-N bond rotamers, but Z-configuration is more stable with the ap-conformation of the C-N bond rotamers. The conformation of C-N bond with equal configuration of C=N bond and equal conformation of N-O bond, sp-form is favored, but the conformation of N-O bond with equal configuration and equal conformation of C-N bond ap-form is more stable. The major part of the stabilization energies can be accounted for by the electrostatic energies between the atoms involved.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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• pp.172-173
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• 2005

The electronic state of ZnO doped with Y was calculated using the density functional theory. In this study, the program used for the calculation on theoretical structures of ZnO and doped ZnO was Vienna Ab-initio Simulation Package (VASP), which is a sort of pseudo potential method. The detail of electronic structure was obtained by the descrite variational $X\alpha$ (DV-$X\alpha$) method, which is a sort of molecular orbital full potential method. The optimized crystal structures obtained by calculations were compared to the measured structure. The density of state and energy levels of dopant elements was shown and discussed in association with optical properties.