• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2335-2339
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• 2013

Relative reactivity of various Al-substituted dialkylalans ($AlR_2(X)$) in reduction of acetone has been studied with density functional theory and MP2 method. Formation of the alan dimers and the alan-acetone adduct, and the transition state for the Meerwein-Ponndorf-Verley (MPV) type reduction of the adduct were calculated to figure out the energy profile. Formation of dimeric alans is highly exothermic. Both the relative free energies for acetone-alan adduct formation and the TS barriers for the MPV type reduction with respect to alan dimers and acetone were calculated and they show the same trend. Based on these energetic data, relative reactivity of alans is expected to be; $AlR_2(Cl)$ > $AlR_2(OTf)$ > $AlR_2(O_2CCF_3)$ > $AlR_2(F)$ > $AlR_2(OMs)$ > $AlR_2(OAc)$ > $AlR_2(OMe)$ > $AlR_2(NMe_2)$. The energy profile is relatively well correlated with the experimental order of the reactivity of Al-substituted dialkylalans. It is noted that the substituents of alans have initial effects on the relative free energies for the carbonyl-adduct formation. Therefore, an $AlR_2(X)$ which forms a more stable carbonyl-adduct is more reactive in carbonyl reduction.

• 한국세라믹학회지
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• 제53권5호
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• pp.521-528
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• 2016

Kinetic Monte Carlo (KMC) and graph searches show that proton conduction limiting barriers and trajectories in $BaZr_{0.875}Y_{0.125}O_3$ are affected by the presence of other protons. At 1000 K, KMC limiting conduction barriers increase from 0.39 eV to 0.45 eV as the proton number is increased. The proton-proton radial distribution begins to rise at $2{\AA}$ and peaks at $4{\AA}$, which is half the distance expected, based on the proton concentration. Density functional theory (DFT) calculations find proton/proton distances of 2.60 and $2.16{\AA}$ in the lowest energy two-proton configurations. A simple average of the limiting barriers for 7-10 step periodic long range paths found via graph theory at 1100 K shows an increase in activation barrier from 0.32 eV to 0.37 eV when a proton is added. Both KMC and graph theory show that protons can affect each other's pathways and raise the overall conduction barriers.

• Korean Chemical Engineering Research
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• 제56권6호
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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.

• 대한화학회지
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• 제63권3호
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• pp.160-165
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• 2019

A series of reactions between an amino alcoholic ligand, cis-2-((2-((2-hydroxyethyl)amino)ethyl)amino)cyclohexan-1-ol (HEAC), with the mixtures of group 12 metals including, $HgCl_2/CdCl_2$, $HgCl_2/CdI_2$, $ZnCl_2/CdCl_2$ and $ZnCl_2/CdCl_2/HgCl_2$ was experimentally and theoretically studied to determine the most stable product of these reactions. Furthermore, the Cambridge Structural Database (CSD) studies were done to evaluate the theoretical results. The products were characterized by elemental analysis, FT-IR, Raman, $^1H$ NMR spectroscopy and single-crystal X-ray diffraction. Based on these investigations a binuclear structure of cadmium, [$Cd_2(HEAC)_2({\mu}-Cl)_2Cl_2$] (1), is the most stable product that was formed in all studied reactions between HEAC and metals mixtures. In this structure, the cadmium atom has a $CdN_2O({\mu}-Cl)_2Cl$ environment and distorted octahedral geometry.

• Advances in nano research
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• 제10권4호
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• pp.339-347
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• 2021

In the framework of the density functional theory combined with the method of non-equilibrium Green functions (DFT + NEGF), the electric transport properties of a one-dimensional nanodevice consisting of telescoping polyprismanes with various types of electrical conductivity were studied. Its transmission spectra, density of state, current-voltage characteristic, and differential conductivity are determined. It was shown that C_[14,17], C_[14,11], C_[14,16], C_[14,10] show a metallic nature, and polyprismanes C_[14,5], C_[14,4] possess semiconductor properties and has a band gap of 0.4 eV and 0.6 eV, respectively. It was found that, when metal C_[14,11], C_[14,10] and semiconductor C_[14,5], C_[14,4] polyprismanes are coaxially connected, a Schottky barrier is formed and a weak diode effect is observed, i.e., manifested valve (rectifying) property of telescoping polyprismanes. The enhancement of this effect occurs in the nanodevices C_[14,17] - C_[14,11] - C_[14,5] and C_[14,16] - C_[14,10] - C_[14,4], which have the properties of nanodiode and back nanodiode, respectively. The simulation results can be useful in creating promising active one-dimensional elements of nanoelectronics.

• Advances in nano research
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• 제10권5호
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• pp.471-479
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• 2021

In the framework of the density functional theory combined with the method of non-equilibrium Green functions (DFT + NEGF), the electric transport properties of a one-dimensional nanodevice consisting of telescoping polyprismanes with various types of electrical conductivity were studied. Its transmission spectra, density of state, current-voltage characteristic, and differential conductivity are determined. It was shown that C_[14,17], C_[14,11], C_[14,16], C_[14,10] show a metallic nature, and polyprismanes C_[14,5], C_[14,4] possess semiconductor properties and has a band gap of 0.4 eV and 0.6 eV, respectively. It was found that, when metal C_[14,11], C_[14,10] and semiconductor C_[14,5], C_[14,4] polyprismanes are coaxially connected, a Schottky barrier is formed and a weak diode effect is observed, i.e., manifested valve (rectifying) property of telescoping polyprismanes. The enhancement of this effect occurs in the nanodevices C_[14,17] - C_[14,11] - C_[14,5] and C_[14,16] - C_[14,10] - C_[14,4], which have the properties of nanodiode and back nanodiode, respectively. The simulation results can be useful in creating promising active one-dimensional elements of nanoelectronics.

• 통합자연과학논문집
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• 제15권4호
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• pp.179-186
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• 2022

The c-Jun N-terminal kinase (JNK3) play major role in neurodegenerative diseases like Alzheimer's disease, Parkinson's disease, cerebral ischemia and other Central Nervous System disorders. Since JNK3 is primarily stated in the brain and stimulated by stress-stimuli, this situation is conceivable that inhibiting JNK3 could be a possible treatment for the mechanisms underlying neurodegenerative diseases. In this study drugs from Zinc15 database were screened to identify the JNK3 inhibitors by Molecular docking and Density functional theory approach. Molecular docking was done by Autodock vina and the ligands were selected based on the binding affinity. Our results identified top ten novel ligands as potential inhibitors against JNK3. Molecular docking revealed that Venetoclax, Fosaprepitant and Avapritinib exhibited better binding affinity and interacting with proposed binding site residues of JNK3. Density functional theory was used to compute the values for energy gap, lowest unoccupied molecular orbital (LUMO), and highest occupied molecular orbital (HOMO). The results of Density functional theory study showed that Venetoclax, Fosaprepitant and Avapritinib serves as a lead compound for the development of JNK3 small molecule inhibitors.

• Nuclear Engineering and Technology
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• 제55권3호
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• pp.895-901
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• 2023

Oxide-dispersion- strengthened nickel alloys with Hf additions are expected to present high temperature mechanical properties and durable helium resistance based on first-principles density functional theory (DFT) calculations. Energetic and charge density evaluations of the helium behaviors were performed in Ni matrix, Y₂Hf₂O₇ oxide and the oxide/matrix interface. With the presence of coherent Y₂Hf₂O₇ in Ni matrix, chances of helium bubbles in Ni can be greatly diminished. The helium atoms shall occupy the interfacial site initially, then diffuse into in the octahedral sites of Y₂Hf₂O₇, and these oxide-captured He atoms prefer to separate individually. Much higher diffusion barrier of He in Y₂Hf₂O₇ than in nickel is related to the strong hybridization between interstitial He-1s and nearest-neighboring O-2p orbitals.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3495-3501
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• 2014

A novel crystal, the mono-protonated metformin acetate (1), was obtained and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. It was found that one of the imino group in the metformin cation was protonated along with the proton transfer from the secondary amino group to the other imino group. Its crystal structure was then compared with the previously reported diprotonated metformin oxalate (2). The difference between them is that the mono-protonated metformin cations can be linked by hydrogen bonding to form dimers while the diprotonated metformin cations cannot. Both of them are stabilized by intermolecular hydrogen bonds to assemble a 3-D supermolecular structure. The four potential tautomer of the mono-protonated metformin cation (tautomers 1a, 1b, 1c and 1d) were optimized and their single point energies were calculated by Density Functional Theory (DFT) B3LYP method based on the Polarized Continuum Model (PCM) in water, which shows that the most likely existed tautomer in human cells is the same in the crystal structure. Based on the optimized structure, their Wiberg bond orders, Natural Population Analysis (NPA) atomic charges, molecular electrostatic potential (MEP) maps were calculated to analyze their electronic structures, which were then compared with the corresponding values of the diprotonated metformin cation (cation 2) and the neutral metformin (compound 3). Finally, the possible tautomeric mechanism of the mono-protonated metformin cation was discussed based on the observed phenomena.

• Advances in nano research
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• 제12권1호
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• pp.25-35
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• 2022

Within the framework of the density functional theory combined with the method of non-equilibrium Green's functions (DFT + NEGF), the features of electron transport in fullerene nanojunctions, which are «core-shell» nanoobjects made of a combination of fullerenes of different diameters C₂₀, C₈₀, C₁₈₀, placed between gold electrodes (in a nanogap), are studied. Their transmission spectra, the density of state, current-voltage characteristics and differential conductivity are determined. It was shown that in the energy range of -0.45-0.45 eV in the transmission spectrum of the "Au-C₁₈₀-Au" nanojunction appears a HOMO-LUMO gap with a width of 0.9 eV; when small-sized fullerenes C₂₀, C₈₀ are intercalation into the cavity C₁₈₀ the gap disappears, and a series of resonant structures are observed on their spectra. It has been established that distinct Coulomb steps appear on the current-voltage characteristics of the "Au-C₁₈₀-Au" nanojunction, but on the current-voltage characteristics "Au-C₈₀@C₁₈₀-Au", "Au-(C₂₀@C₈₀)@C₁₈₀-Au" these step structures are blurred due to a decrease in Coulomb energy. An increase in the number of Coulomb features on the dI/dV spectra of core-shell fullerene nanojunctions was revealed in comparison with nanojunctions based on fullerene C₆₀, which makes it possible to create high-speed single-electron devices on their basis. Models of single-electron transistors (SET) based on fullerene nanojunctions "Au-C₁₈₀-Au", "Au-C₈₀@C₁₈₀-Au" and "Au-(C₂₀@C₈₀)@C₁₈₀-Au" are considered. Their charge stability diagrams are analyzed and it is shown that SET based on C₈₀@C₁₈₀-, (C₂₀@C₈₀)@C₁₈₀- nanojunctions is output from the Coulomb blockade mode with the lowest drain-to-source voltage.