• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.453-456
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• 2010

The structural and energetic preferences of thiacalix[4]biscrown-5 with and without alkali metal ions ($Na^+$, $K^+$, $Rb^+$, and $Cs^+$) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-$\pi$ interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2093-2098
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• 2013

Density functional theory (DFT) was used to determine the ground state geometries of indigo and new design dyes (IM-Dye-1 IM-Dye-2 and IM-Dye-3). The time dependant density functional theory (TDDFT) was used to calculate the excitation energies. All the calculations were performed in both gas and solvent phase. The LUMO energies of all the dyes were above the conduction band of $TiO_2$, while the HOMOs were below the redox couple (except IM-Dye-3). The HOMO-LUMO energy gaps of new design dyes were smaller as compared to indigo. All new design dyes were strongly red shifted as compared to indigo. The improved light harvesting efficiency (LHE) and free energy change of electron injection ${\Delta}G^{inject}$ of new designed sensitizers revealed that these materials would be excellent sensitizers. The broken coplanarity between the benzene near anchoring group having LUMO and the last benzene attached to TPA unit in all new design dyes consequently would hamper the recombination reaction. This theoretical designing will the pave way for experimentalists to synthesize the efficient sensitizers for solar cells.

• Korean Journal of Materials Research
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• v.18 no.9
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• pp.482-485
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• 2008

Tetragonal-$Ni_{1-x}Pd_x$Si/Si (001) structure was studied by using density functional theory (DFT). An epitaxial interface between $2{\times}2{\times}4$ (001) tetragonal-NiSi supercell and $1{\times}1{\times}2$ (001) Si supercell was first constructed by adjusting the lattice parameters of B2-NiSi structure to match those of the Si structure. We chose Ni atoms as a terminating layer of the B2-NiSi; the equilibrium gap between the tetragonal-NiSi and Si was calculated to be 1.1 ${\AA}$. The Ni atoms in the structure moved away from the original positions along the z-direction in a systematic way during the energy minimization. Two different Ni sites were identified at the interface and the bulk, respectively. The two Ni sites at the interface have 6 and 7 coordination numbers. The Ni sites with coordination number 6 at the interface were located farther away from the interface, and were more favorable for Pd substitution.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2219-2222
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• 2010

A density functional theory (DFT) study of $CO_2$ adsorption on barium oxide (BaO) adsorbents is conducted to understand the chemical activity of the oxygen site on the BaO (100) surface. This study evaluated the adsorption energies and geometries of a single $CO_2$ molecule and a pair of $CO_2$ molecules on the BaO (100) surface. A quantum calculation was performed to obtain information on the molecular structures and molecular reaction mechanisms; the results of the calculation indicated that $CO_2$ was adsorbed on BaO to form a stable surface carbonate with strong chemisorption. To study the interactive $CO_2$ adsorption on the BaO (100) surface, a pair of $CO_2$ molecules was bound to neighboring and distant oxygen sites. The interactive $CO_2$ adsorption on the BaO surface was found to slightly weaken the adsorption energy, owing to the interaction between $CO_2$ molecules.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.211.1-211.1
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• 2014

Recently, the scaling of conventional planar NAND flash devices is facing its limits by decreasing numbers of electron stored in the floating gate and increasing difficulties in patterning. Three-dimensional vertical NAND devices have been proposed to overcome these issues. Atomic layer deposition (ALD) is the most promising method to deposit charge trap layer of vertical NAND devices, SiN, with excellent quality due to not only its self-limiting growth characteristics but also low process temperature. ALD of silicon nitride were studied using NH3 and silicon chloride precursors, such as SiCl4[1], SiH2Cl2[2], Si2Cl6[3], and Si3Cl8. However, the reaction mechanism of ALD silicon nitride process was rarely reported. In the present study, we used density functional theory (DFT) method to calculate the reaction of silicon chloride precursors with a silicon nitride surface. DFT is a quantum mechanical modeling method to investigate the electronic structure of many-body systems, in particular atoms, molecules, and the condensed phases. The bond dissociation energy of each precursor was calculated and compared with each other. The different reactivities of silicon chlorides precursors were discussed using the calculated results.

• 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.

• Nuclear Engineering and Technology
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• v.49 no.8
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• pp.1748-1751
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• 2017

Reduced activation ferritic/martensitic (RAFM) steels are widely applied as structural materials in the nuclear industry. To investigate hydrogen's effect on RAFM steels' elastic properties and the mechanism of that effect, a procedure of first principles simulation combined with experiment was designed. Density functional theory models were established to simulate RAFM steels' elastic status before and after hydrogen's insertion. Also, experiment was designed to measure the Young's modulus of RAFM steel samples with and without hydrogen charging. Both simulation and experiment showed that the solubility of hydrogen in RAFM steels would decrease the Young's modulus. The effect of hydrogen on RAFM steels' Young's modulus was more significant in water-quenched steels than it was in tempering steels. This indicated that defects inside martensite, considered to be hydrogen traps, could decrease the cohesive energy of the matrix and lead to a decrease of the Young's modulus after hydrogen insertion.

• Korean Journal of Materials Research
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• v.27 no.4
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• pp.229-235
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• 2017

Through density functional theory calculations, to provide insight into the origins of the catalytic activity of Au nanoparticles (NPs) toward oxidation reactions, we have scrutinized the oxygen adsorption chemistry of 9 types of small unsupported Au NPs of around 1 nm in size (Au13, Au19, Au20, Au25, Au38, and Au55) looking at several factors (size, shape, and coordination number). We found that these NPs, except for the icosahedral Au13, do not strongly bind to $O_2$ molecules. Energetically most feasible $O_2$ adsorption that potentially provides high CO oxidation activity is observed in the icosahedral Au13, our smallest Au NP. In spite of the chemical inertness of bulk Au, the structural fluxionality of such very small Au NP enables strong $O_2$ adsorption. Our results can support recent experimental findings that the exceptional catalytic activity of Au NPs comes from very small Au species consisting of around 10 atoms each.

• Journal of the Korean Ceramic Society
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• v.52 no.5
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• pp.331-337
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• 2015

$LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

• Journal of the Semiconductor & Display Technology
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• v.20 no.4
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• pp.16-22
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• 2021

We search for an appropriate initial adsorption coordination of precursor on surface by using genetic algorithm (GA) and density functional theory. SiH₄ and Al(CH₃)₃ as precursor, and OH-terminated Si (001) as surface are used for this study. Selection, crossover, and mutation as hyperparameters of GA are applied to search for the adsorption coordination of the precursors on the surface as a function of generation. Bond distances between precursors and the surface are used to explain the adsorption behavior of the precursors.