• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.100-104
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• 2011

The structures of the conformers for 1,3-di-t-butyl-2,4-dinitro-tetramethoxysulfonylcalix[4]arene (1) and 1,2-di-t-butyl-3,4-dinitro-tetramethoxysulfonylcalix[4]arene (2) were optimized using DFT BLYP and mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the total electronic and Gibbs free energies and the differences between the various conformations (cone, partial-cone (PC), 1,2-alternate, and 1,3-alternate) of 1 and 2. For both compounds, the 1,3-alternate (1,3-A) conformers were calculated to be the most stable, which correlate very well with the experimental results. The orderings of the relative stability of 1 and 2 that resulted from the mPW1PW91/6-31G(d,p) calculations are the following: 1: 1,3-A (syn) > PC (syn) > PC (anti) > 1,2-A (anti) > CONE (syn); 2: 1,3-A (anti) > PC (anti) > PC (syn) > 1,2-A (anti) > 1,2-A (syn) > CONE (syn). The BLYP/6-31G(d) calculated IR spectra of the most stable 1,3-A conformers of 1 and 2 are compared.

• Journal of Environmental Science International
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• v.16 no.7
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• pp.855-863
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• 2007

In order to understand the temporal distribution of pico- and nanoplankton and factors controlling its distribution at a station in Okkye Bay of Masan Bay located in the southern part of Korea, this study was conducted on two weeks interval from April 2005 to April 2006, and several abiotic and biotic factors were measured. During the study, picoplankton consisted of picoflagellates, cyanobacteria and heterotrophic bacteria, and nanoplankton consisted of nanoflagellates excluding dinoflagellates. The concentration of chlorophyll-a (chl-a) was a mean of $4.33\;{\mu}g/L$, and the nanoplanktonic ($<20\;{\mu}m$) chl-a size fraction was a mean of 39.5 % and significantly correlated with water temperature. The abundances of cyanobacteria and photosynthetic flagellates (PF) were means of $24.4{\times}10^{3}\;cells/mL\;and\;2.87{\times}10^{3}\;cells/mL$, respectively. The contribution of picoflagellates to the PF abundance varied among the sampling occasions and was a mean of 29 %, but to the PF carbon biomass was 2.6 % only. The PF abundance had significant relationships with water temperature, and silicate and TIN concentrations, suggesting that the PF abundance seemed to be primarily bottom-up regulated. The abundance of heterotrophic bacteria was a mean of $3.18{\times}10^{6}\;cells/mL$ and unlike other ecosystems it did not have relationships with chl-a and heterotrophic flagellates (HF), suggesting that bacterial abundance did not seem to be bottom-up or top-down regulated. HF mostly consisted of cells less than $5{\mu}m$ and its abundance was a mean of $2.71{\times}10^{3}\;cells/mL$. Of the HF abundance, picoflagellates occupied about 31 %, and occupied about 9 % of the HF carbon biomass. HF grazing activity on heterotrophic bacteria was relatively low and removed about 10 % of bacterial abundance, suggesting that HF might not be major consumers of bacteria and there seems to be other consumers in Okkye Bay. These results suggest that Okkye Bay may have a unique microbial ecosystem.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.48 no.6
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• pp.1-6
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• 2011

A transparent oxide thin film transistors (Transparent Oxide-TFT) have been fabricated by RF magnetron sputtering at room temperature using amorphous indium zinc oxide (a-IZO) as both of active channel and source/drain, gate electrodes and co-sputtered $HfO_2-Al_2O_3$ (HfAIO) as gate dielectric. In spite of its high dielectric constant > 20), $HfO_2$ has some drawbacks including high leakage current and rough surface morphologies originated from small energy band gap (5.31eV) and microcrystalline structure. In this work, the incorporation of $Al_2O_3$ into $HfO_2$ was obtained by co-sputtering of $HfO_2$ and $Al_2O_3$ without any intentional substrate heating and its structural and electrical properties were investigated by x-ray diffraction (XRD), atomic force microscopy (AFM) and spectroscopic ellipsometer (SE) analyses. The XRD studies confirmed that the microcrystalline structures of $HfO_2$ were transformed to amorphous structures of HfAIO. By AFM analysis, HfAIO films (0.490nm) were considerably smoother than $HfO_2$ films (2.979nm) due to their amorphous structure. The energy band gap ($E_g$) deduced by spectroscopic ellipsometer was increased from 5.17eV ($HfO_2$) to 5.42eV (HfAIO). The electrical performances of TFTs which are made of well-controlled active/electrode IZO materials and co-sputtered HfAIO dielectric material, exhibited a field effect mobility of more than $10cm^2/V{\cdot}s$, a threshold voltage of ~2 V, an $I_{on/off}$ ratio of > $10^5$, and a max on-current of > 2 mA.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3247-3251
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• 2010

Molecular structures of the various conformers for the four stereoisomers of tetra-t-butyl-tetra-O-methylsulfinylcalix[4]arene (1) were optimized using DFT BLYP and mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the total electronic and Gibbs free energies and normal vibrational frequencies of 16 different structures from four major conformations (cone (CONE), partial cone (PC), 1,2-alternate (1,2-A), 1,3-alternate (1,3-A)) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), 1(rtct)]. The mPW1PW91/6-31G(d,p) calculations suggested that the $1(rccc)_{CONE}$, $1(rcct)_{PC}$, $1(rctt)_{PC}$, and $1(rtct)_{1,3-A}$ were the most stable conformations of the respective stereoisomers. These outcomes are in accordance with the experimental structures obtained from X-ray crystallography. The electrostatic repulsion between the sulfinyl and methoxy groups is a primary factor for the relative stabilities of the four different conformations. The IR spectra of the most stable conformers [$1(rccc)_{CONE}$, $1(rcct)_{PC}$, $1(rctt)_{PC}$, $1(rtct)_{1,3-A}$] of each stereoisomer were compared to each other.

• Proceedings of the PSK Conference
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• 2003.10b
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• pp.158.1-158.1
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• 2003

We report here the results on N-acetyl-N"-methylamide of oxazolidine (Ac-Oxa-NHMe) calculated using the ab initio molecular orbital method with the self-consistent reaction field (SCRF) theory at the HF level of theory with the 6-31 +G(d) basis set. The displacement of the $\gamma$-$CH_2$ group in proline ring by oxygen atom has affected the structure of proline, cis-trans equilibrium, and rotational barrier. The up-puckered structure is found to be prevalent for the trans conformers of the Oxa amide. (omitted)

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.640-652
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• 2009

We have performed mPW1PW91 calculations to investigate the conformational characteristics and hydrogen bonds of p-tert-butylcalix[4]arene (1), p-tert-butylcalix[5]arene (2), calix[6]arene (3) and p-tertbutylcalix[6]arene (4). The structures of the different conformers of 1-3 were optimized by using mPW1PW91/6-31+G(d,p) method. The relative stability of the four conformers of 1 is in the following order: cone (most stable) > partial-cone > 1,2-alternate > 1,3-alternate. The relative stability of the conformers of 2 is in the following order: cone (most stable) > 1,2-alternate > partial-cone > 1,3-alternate. The relative stability of the various conformers of 3 is in the following order: cone (pinched: most stable) > partial-cone > cone (winged) - 1,2-alternate - 1,2,3-alternate > 1,4-alternate > 1,3-alternate > 1,3,5-alternate. The structures of the various conformers of 4 were optimized by using the mPW1PW91/6-31G(d,p) method followed by single point calculation of mPW1PW91/6-31+G(d,p). The relative stability of the conformers of 4 is in the following order: cone (pinched) > 1,2-alternate > cone (winged) > 1,4-alternate - partial-cone > 1,2,3-alternate > 1,3,5-alternate > 1,3-alternate. The primary factor affecting the relative stabilities of the various conformers of the 1-4 are the number and strength of the intramolecular hydrogen bonds. The hydrogen-bond distances are discussed based on two different calculation methods (B3LYP and mPW1PW91).

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• 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.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.891-896
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• 2002

The structures and energies of p-tert-butylcalix[4]crown-6-ether(1) in various conformers and their alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. We have tried to obtain the relative affinity of partial-cone and 1,3-alternate conformers of 1 for alkyl ammonium guests by comparison with its cone-shaped analogue. We have also calculated the relative complexation efficiency of these host-guest complexes focusing on the binding sites of $crown-\sigma-enther$ moiety or benzene-rings pocket of the host molecule 1. These calculations revealed that the crown moiey has better complexation efficiency than upper rim part of calyx[4]arene that is in similar trend to the cone-shaped complexes.

• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.989-993
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• 2014

The molecular structures of 2,6-diaza-1,3,5,7-tetraoxaspiro[3,3]heptane (1) and its dinitro derivative, 2,6-dinitro-2,6-diaza-1,3,5,7-tetraoxaspiro[3,3]heptane (2), were fully optimized without symmetry constraints at $HF/6-31G^*$ level of theory. A bisected conformation with respect to the ring is preferred with a $C_2$ symmetric structure. The density of each molecule in the crystalline state was estimated to 1.12 and 2.36 $g/cm^3$ using PM3/VSTO-3G calculations from the molecular volume. The heat of formation was calculated for two compounds at the CBS-4M level of theory. The detonation parameters were computed using the EXPLO5 software: D = 6282 m/s, $P_{C-J}$ = 127 kbar for compound 1, D = 7871 m/s, $P_{C-J}$ = 307 kbar for compound 2, and D = 6975 m/s, $P_{C-J}$ = 170 kbar for 60% compound 2 with 40% TNT. Specific impulse of compound 1 in aluminized formulation when used as monopropellants was very similar to that of the conventional ammonium perchlorate in the same formulation of aluminum.