• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.704-710
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• 2004

A poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) (PHDP) was prepared and its luminescence in tetrahydrofuran (THF) was studied. When PHDP is excited by UV light, it produces very strong blue luminescence. The quantum yield of PHDP (Q = 36.9%) is much greater than that of the monomer, 1-hexyl-3,4-dimethylpyrrole (HDP) with Q = 0.61%. The principal luminescence of PHDP has a single decay component with ca. 1 ns, whereas the decay of HDP is complicated. The molecular structure and conformational behavior of HDP and the oligomers up to trimer have been also determined by ab initio Hartree-Fock (HF/6-31$G^{**}$), density functional theory (DFT-B3LYP/6-31$G^{**}$), and semiempirical (ZINDO) methods. According to the results of calculations, it is proposed that the enhanced quantum yield of the polymer PHDP results mostly from the ${\pi}$-conjugation between neighboring pyrrole rings.

• 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.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.97-97
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• 2016

Development of advanced Li-ion battery cells with high durability is critical for safe operation, especially in applications to electric vehicles and portable electronic devices. Understanding fundamental mechanism on the formation of a solid-electrolyte interphase (SEI) layer, which plays a substantial role in the electrochemical stability of the Li-ion battery, in a cathode was rarely reported unlike in an anode. Using first-principles density functional theory (DFT) calculations and ab-initio molecular dynamic (AIMD) simulations we demonstrate atomic-level process on the generation of the SEI layer at the interface of a carbonate-based electrolyte and a spinel $LiMn_2O_4$ cathode. To accomplish the object we calculate the energy band alignment between the work function of the cathode and frontier orbitals of the electrolyte. We figure out that a proton abstraction from the carbonate-based electrolyte is a critical step for the initiation of an SEI layer formation. Our results can provide a design concept for stable Li-ion batteries by optimizing electrolytes to form proper SEI layers.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.452-452
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• 2011

Using ab initio calculations, we reveal the origins of the extraordinarily increased electric conductivity of the LaAlO3/SrTiO3 interface. In both of the two (LaAlO3)m/ SrTiO3 heterojunction models (m=3, 5), the oxygen atoms in the cells were displaced toward the n-type interface and the Ti-centered octahedron structure was compressed along the [001] direction by the atomic reconstructions at the (LaAlO3)m/(SrTiO3)4 interfaces. As a result, the 3dxy orbital of the Ti atom was preferentially occupied due to the lowered energy state of the 3dxy orbital, which arises from the crystal field asymmetry. We reason that the extra electrons occupy the 3dxy orbital are accumulated at the interface by the displacement of the oxygen atoms. This accumulation contributes to the conductivity of the n-type interface. In addition, through a comparison of the atomic displacements and charge accumulation amounts between the two thickness models (m=3, 5), the thickness-dependency of the conductivity can be explained.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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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.

• Bulletin of the Korean Chemical Society
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• v.24 no.6
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• pp.864-880
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• 2003

A unified picture for magnetism, superconductivity, quantum optics and other properties of molecule-based materials has been presented on the basis of effective model Hamiltonians, where necessary parameter values have been determined by the first principle calculations of cluster models and/or band models. These properties of the matetials are qualitatively discussed on the basis of the spin and pseudo-spin Hamiltonian models, where several quantum operators are expressed by spin variables under the two level approximation. As an example, ab initio broken-symmetry DFT calculations are performed for cyclic magnetic ring constructed of 34 hydrogen atoms in order to obtain effective exchange integrals in the spin Hamiltonian model. The natural orbital analysis of the DFT solution was performed to obtain symmetry-adapted molecular orbitals and their occupation numbers. Several chemical indices such as information entropy and unpaired electron density were calculated on the basis of the occupation numbers to elucidate the spin and pair correlations, and bonding characteristic (kinetic correlation) of this mesoscopic magnetic ring. Both classical and quantum effects for spin alignments and singlet spin-pair formations are discussed on the basis of the true spin Hamiltonian model in detail. Quantum effects are also discussed in the case of superconductivity, atom optics and quantum optics based on the pseudo spin Hamiltonian models. The coherent and squeezed states of spins, atoms and quantum field are discussed to obtain a unified picture for correlation, coherence and decoherence in future materials. Implications of theoretical results are examined in relation to recent experiments on molecule-based materials and molecular design of future molecular soft materials in the intersection area between molecular and biomolecular materials.

• Journal of the Korean Chemical Society
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• v.59 no.3
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• pp.209-214
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• 2015

The formation of complexes between SO₂ and acetic acid was studied theoretically. The ab initio and DFT calculations were performed with MP2 and B3LYP methods using 6-311++G(d,p), aug-cc-pVDZ and aug-cc-pVTZ basis sets. Six stable complexes were identified, and three stable bidentate complexes, C1, C2 and C3, were formed between SO₂ and syn-acetic acid, which is more stable form of acetic acid. Anti-acetic acid also form three complexes, C4, C5 and C6, with SO₂. C4 is bidentate and C5, C6 are monodentate complexes, which are less stable. The most stable complex, C1 has S⋯O=C and O⋯H-O interactions, and the S⋯O and O⋯H distances are less than the sum of van der Waals radii. The vibrational frequencies of complexes were calculated and were compared with those of monomers. The frequency shifts after formation of complex were found, and the overall pattern of frequency shifts relative to monomers is similar among the six complexes.