• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.69-75
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• 2008

Tautomerism of pyrimidine base cytosine has been comparatively examined on nanoparticle and roughened plate surfaces of silver, gold, and copper by surface-enhanced Raman scattering (SERS). The SERS spectrum was found to be different depending on the metals and their substrate conditions suggesting the dissimilar population of various tautomers of cytosine on the surfaces. The ab initio calculations were performed at the levels of B3LYP, HF, and MP2 levels of theory with the LanL2DZ basis set to estimate the energetic stability of the tautomers with the metal complexes as well as the gas phase state. The amino group and N3-coordinated tautomer was predicted to be more favorable for bonding to Au, whereas the hydroxyl and N1-coordinated zwitter ionic form is most stable with Ag and Cu as a bidentate form from the DFT calculation. The binding energy with the Ag atom is calculated to be smaller than those with the Au and Cu atoms in line with the temperature-dependent SERS spectra of cytosine.

• Transactions on Electrical and Electronic Materials
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• v.17 no.1
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• pp.29-32
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• 2016

Using the various exchange-correlation functionals, such as LDA, GGA-PBE, GGA-PBEsol and GGA-AM05 functionals, first principle studies were conducted to determine the structures of paraelectric and ferroelectric PbTiO₃. Based on the structures determined by the various functionals, the piezoelectric properties of PbTiO₃ are predicted under the density-functional perturbation theory (DFPT). The present prediction with the various GGA functionals are closer to the experimental findings compared to the LDA values. The present DFT calculations using the GGA-PBEsol functional estimate the experimental data more reasonably than the conventional LDA and GGA fucntionals. The GGA-AM05 functional also predicts the experimental data as well as the GGA-PBEsol. The piezoelectric tensor calculated with PBEsol is relatively insensitive to pressure.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.107-108
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• 2008

We calculated orthorhombic-NiSi (010)/Si superstructure. Orthorhombic-NiSi was changed to tetragonal structure to be matched with Si substrate. Eight models were produced by the type of Si substrate. In the case of orthorhombic-NiSi (010)/Si (020)[00-1], it was the most favorable energetically and the shortest of the distance between two superstructures. However, in the case of orthorhombic-NiSi (010)/Si (010)[00-1], it was the most unfavorable energetically and the longest of the distance. The energy and distance of orthorhombic-NiSi (010)/Si superstructure were changed by the coordination number of Ni atom and the bond length of atom-atom at the interface.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.22 no.5
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• pp.377-381
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• 2009

Tetragonal-NiSi (010)/Si superstructures were calculated for studying the interface structure using density functional theory, The orthorhombic-NiSi was changed to the tetragonal-NiSi to be matched with the Si surface for epitaxy interface. The eight interface models were produced by the type of the Si surfaces, The tetragonal-NiSi (010)/Si (020)[00-1] superstructure was energetically the most favorable, and the interface thickness of this superstructure was the shortest among the tetragonal-NiSi (010)/Si superstructures. However, in the case of tetragonal-NiSi (010)/Si (010)[00-1] superstructure, it was energetically the most unfavorable, and the interface thickness was the longest. The energies and interface thicknesses of tetragonal-NiSi (010)/Si superstructures were influenced by the coordination number of Ni atoms and the bond length between atoms located at the interface.

• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.909-913
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• 2018

A hydrocarbon trap (HT) plays an important role of controlling vehicle emissions in the so-called cold emission period by holding hydrocarbons until three way catalysts (TWCs) are thermally activated. In this study, we have investigated the adsorption characteristics of cation (H, La, K, and Ag)-exchanged ZSM-5 zeolites for hydrocarbons (propylene, n-butane, and toluene) by DFT (density functional theory)-based computational chemistry. Cation exchange is to improve the hydrothermal stability of zeolites and their adsorption capacity, thereby rendering cation-exchanged zeolites promising materials for HT. The idea of cluster approximation makes the calculation of adsorption energies superbly efficient in computation. The results showed that Ag-exchanged ZSM-5 would be the best for the adsorption of all three adsorbates, without often encountered Ag oxidation in experiments. Besides, the hydrothermal stability of La-exchanged ZSM-5 was confirmed from the change of geometrical parameters by cation exchange, and it showed good adsorption capacity for propylene and toluene. Hydrogen-exchanged ZSM-5 was also good for hydrogen adsorption, but had poor hydrothermal stability.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.212-212
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• 2012

The Coverage dependent attachment of multifunctional groups included in threonine molecules adsorbed to Ge (100)$-2{\times}1$ surface was investigated using core-level photoemission spectroscopy (CLPES) and density functional theory (DFT) calculations. The core-level spectra at a low coverage indicated that the both carboxyl and amine groups participated in the bonding with the Ge (100) surface by "O-H dissociated and N-dative bonded structure". However, at high coverage level, additional adsorption geometry of "O-H dissociation bonded structure" appeared possibly to minimize the steric hindrance between adsorbed molecules. Moreover, the C 1s, N 1s, and O 1s core level spectra confirmed that the carboxyl oxygen is more competitive against the hydroxymethyl oxygen in the adsorption reaction. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. Conclusively, we investigate in threonine on Ge (100) surface system that the "O-H dissociated-N dative bonded structure" and the "O-H dissociation bonded structure" are preferred at low coverage and high coverage.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.182-182
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• 2011

We investigated the adsorption structures of serine on a Ge(100) surface by core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. The core-level C 1s, N 1s, and O 1s CLPES spectra confirmed that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction, thereby favoring formation of the "O-H dissociated-N dative bonded" and "O-H dissociation bonded" structures at 0.30 ML and 0.60 ML, respectively. The experimental results were corroborated theoretically by calculating the reaction pathways leading to the two adsorption geometries. The reaction pathways indicated that the "O-H dissociated-N dative bonded structure" is the major product of serine adsorption on Ge(100) due to comparably stable adsorption energy.

• Journal of the Korean Electrochemical Society
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• v.16 no.3
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• pp.177-183
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• 2013

As the development of available binder in the harsh conditions is needed, we propose the proper binder for high-voltage lithium-ion secondary batteries based on the quantum chemistry modeling. The optimized structures, HOMO (Highest Occupied Molecular Orbital) energies and ionization potentials of 4 binders, which were considered from monomer to tetramer, were investigated by the semi-empirical and DFT (Density Functional Theory) calculations. The results show that the ionization potential values by calculation tend to be close to the oxidation potentials from the measurement of linear sweep voltametry (LSV). The order of oxidative resistance from high value to low value is following: poly(hexafluropropylene), poly(vinylidene fluoride), poly(methyl acrylate) and poly(acryl amide). Also these results correspond with the experimental values. Thus, we find the reason why HOMO (Highest Occupied Molecular Orbital) energy of PHFP has the highest value than other binders by analysis of HOMO orbital structures.

• Applied Science and Convergence Technology
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• v.25 no.1
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• pp.19-24
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• 2016

In this study, we evaluated the change of electronic structure during redox process in cerium-doped $ZrO_2$ grown by sol gel method. By sol-gel method, we could obtain cerium-doped $ZrO_2$ in high oxygen partial pressure and low temperature. After post annealing process in nitrogen ambient, the film is deoxidized. We used spectroscopic and theoretical methods to analysis change of electronic structure. X-ray absorption spectroscopy (XAS) for O K1-edge and Density Functional Theory (DFT) calculation using VASP code were performed to verify the electronic structure of the film. Also, high resolution x-ray photoelectron spectroscopy (HRXPS) for Ce 3d was carried out to confirm chemical bond of cerium doped $ZrO_2$. Through the investigation of the electronic structure, we verified as followings. (1) During reduction process, binding energy of oxygen is increase. Simultaneously, oxidation state of cerium was change to 4+ to 3+. (2) Cerium 4+ and cerium 3+ states were generated at different energy level. (3) Absorption states in O K edge were mainly originated by Ce 4+ $f_0$ and Ce 3+, while occupied states in valance band were mainly originated from Ce 4+ $f_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.109-110
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• 2008

We have performed a density functional theory study to investigate the reaction of the $HfCl_4$ molecule on $H_2O$ terminated Si (001)-$(2\times1)$ surface. The reaction of the $HfCl_4$ molecule is more favorable on OH-terminated site than H-terminated site. The first $HfCl_4$ molecule is adsorbed on a OH-terminated site with 0.21 eV energy benefit. The second $HfCl_4$ molecule is adsorbed on the most adjacent OH-terminated site of the first molecule and the energy benefit is 0.28 eV. The third and forth molecules have same tendency with the first and second ones. The adsorption energies of the fifth and sixth $HfCl_4$ molecules are 0.01 eV, -0.06 eV respectively. Therefore, we find that the saturation Hf coverage is approximately 5/8 of the available hydroxyl site, which is $2.08\times10^{14}/cm^2$. Our model is well matched with an experimental study by reference.