• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.899-904
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• 2014

The atomic structures and electronic properties of six classical and nonclassical $H_2O$@$C_{24}$ fullerene regioisomers are systematically studied using the hybrid density functional B3LYP method and M06-2X method with empirical dispersion in conjunction with the 6-31G(d,p) basis sets. The charge transfer, frontier orbitals, dipole moment, energy gap between the HOMO and LUMO, and volume change of the $C_{24}$ cage are analyzed upon encapsulation of a $H_2O$ molecule in each $C_{24}$ regioisomer. All encapsulation processes are endothermic and the relative stabilities of six $C_{24}$ fullerene regioisomers change upon encapsulation of $H_2O$.

• Bulletin of the Korean Chemical Society
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• 제31권4호
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• pp.881-886
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• 2010

A novel Schiff base N-(2,4-dinitro-phenyl)-N'-(1-phenyl-ethylidene)-hydrazine has been synthesized and structurally characterized by X-ray single crystal diffraction, elemental analysis, IR spectra and UV-vis spectrum. The crystal belongs to monoclinic with space group P21/n. The molecules are connected via intermolecular O-$H{\cdots}O$ hydrogen bonds into 1D infinite chains. The crystal structure is consolidated by the intramolecular N-$H{\cdots}O$ hydrogen bonds. weak intermolecular C-$H{\cdots}O$ hydrogen bonds link the molecules into intriguing 3D framework. Furthermore, Density functional theory (DFT) calculations of the structure, stabilities, orbital energies, composition characteristics of some frontier molecular orbitals and Mulliken charge distributions of the title compound were performed by means of Gaussian 03W package and taking B3LYP/6-31G(d) basis set. The time-dependent DFT calculations have been employed to calculate the electronic spectrum of the title compound, and the UV-vis spectra has been discussed on this basis. The results show that DFT method at B3LYP/6-31G(d) level can well reproduce the structure of the title compound.

• 한국근적외분광분석학회:학술대회논문집
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• 한국근적외분광분석학회 2001년도 NIR-2001
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• pp.1274-1274
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• 2001

An anharmonicity is a fundamental quantity shaping the potential for stretching OH vibration in phenol and its derivatives. The phenomenon is examined both by experimental and theoretical methods. FT-IR and NIR spectra of series of phenols derivatives were measured in the range of fundamental and first two Overtones of $_{s}(OH)$ Vibrations in $CCl_4$ solutions. The electronic influence of substituents on the analyzed frequencies is discussed and correlated with $pK_{a}$ parameters. Ab initio MP2/6-31G(d,p) and B3LYP/6-31G(g,p) calculations of the potential for proton movement in OH group were performed. Equilibrium structures were also determined. The frequencies of fundamental and overtones were calculated by Numerov-type procedure. The results of calculations are compared with the experimental data. The best linear correlations were obtained for the results of MP2/6-31G(d,p) calculations. It was shown that some structural parameters are especially sensitive on substitution. The linear correlations were found between those parameters and spectroscopic data. The results of calculation are compared with available crystallographic data.

• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1097-1101
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• 2003

The cubic and quartic anharmonic force field of malonaldehyde is calculated using density functional theory at the B3LYP/6-31G(d,p) level, and used to simulate coherent infrared vibrational spectra. 12 normal modes are included in the simulation, and the Arnoldi method is employed for the diagonalization of the Hamiltonian. The calculated three pulse infrared signals in the k1 + k2 - k3 direction show signatures of the intramolecular hydrogen bond couplings between the C=O stretch, H-O-C bend and O-H stretch vibrations.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1043-1049
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• 2014

Density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) theoretical level were performed for two novel explosives (compounds B and C) based on the guanidine-fused bicyclic skeleton $C_4N_6H_8$ (A). The heats of formation (HOFs) were calculated via isodesmic reaction. The detonation properties were evaluated by using the Kamlet-Jacobs equations. The bond dissociation energies (BDEs) for the thermolysis initiation bond were also analyzed to investigate the thermal stability. The results show that the compounds have high positive HOF values (B, 1064.68 $kJ{\cdot}mol^{-1}$; C, 724.02 $kJ{\cdot}mol^{-1}$), high detonation properties (${\rho}$, D and P values of 2.04 $g{\cdot}cm^{-3}$ and 2.21 $g{\cdot}cm^{-3}$, 9.98 $km{\cdot}s^{-1}$ and 10.99 $km{\cdot}s^{-1}$, 46.44 GPa and 59.91 Gpa, respectively) and meet the basic stability requirement. Additionally, feasible synthetic routes of the these high energy density compounds (HEDCs) were also proposed via retrosynthetic analysis.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2633-2636
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• 2010

3-Acetyl-5-benzoyl-6-methyl-2-phenyl-4H-pyran-4-one has been subjected to condensation with a series of primary amines (ethylamine - octylamine) to clarify the proposed mechanism in our previous study. The reactions of the shorter amines of the series (ethylamine - butylamine) yielded unsymmetric pyridinone products, whereas the other amines (pentylamine - octylamine) yielded symmetrical pyridinones. The starting material and the products as well as the intermediates have been subjected to theoretical analysis by quantum chemical calculations at B3LYP/6-31G(d,p) level, which provided supporting data for the experimental findings.

• Bulletin of the Korean Chemical Society
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• 제33권6호
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• pp.1913-1918
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• 2012

The nitramine explosives with $-NH_2$ and -F groups were optimized to obtain their molecular geometries and electronic structures at DFT-B3LYP/6-31+G(d) level. The theoretical molecular density (${\rho}$), heat of formation (HOF), detonation velocity ($D$) and detonation pressure ($P$), estimated using Kamlet-Jacobs equations, showed that the detonation properties of these compounds were excellent. Based on the frequencies scaled by 0.96 and the principle of statistic thermodynamics, the thermodynamic properties were evaluated, which were respectively related with the temperature. The simulation results reveal that 1,3,5,7-tetranitro-1,3,5,7-tetrazocan-2-amine (molecule B1) performs similarly to the famous explosive HMX, and 2-fluoro-1,3,5-trinitro-1,3,5-triazinane (molecule C1) and 2-fluoro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (molecule D1) outperform HMX. According to the quantitative standard of energetics and stability as an HEDC (high energy density compound), molecules C1 and D1 essentially satisfy this requirement. These results provide basic information for molecular design of novel high energetic density compounds.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2403-2407
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• 2013

The hybrid density-functional (B3LYP/6-31G(d,p)) method was used to analyze the substitution effect on the $C_{20}H_{20}$ cage based on calculation of the frontier orbitals of fifteen $C_{20}H_{17}(OH)_3$ derivatives. All substitution products were geometrically optimized without constraints and confirmed by frequency analysis. The results suggest that the cis-1 cis-1 cis-2 regioisomer is the most stable isomer, which implies that hydrogen bonding exerts a stronger effect on the relative energies of the trihydroxide than long-range interactions. Thus, this supports the experimental result in which the bisvicinal tetrol was of particular preparative-synthetic interest. While the LUMO of each of the $C_{20}H_{17}(OH)_3$ regioisomers was equivalently delocalized over the void within the cage, the HOMO was limitedly delocalized on substituents and carbons in close proximity to the substituents. The characteristics of the HOMO of each of the regioisomers vary based on the substitution sites. This indicates that the 15 regioisomers of each $C_{20}H_{20}$ trisubstituted derivative might undergo an entirely different set of characteristic chemical reactions with electrophilic reagents. The results further suggest that the penta-substituted OH groups on the surface of the fullerene cage are more likely to be localized on a pentagon than to be homogeneously delocalized.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3632-3638
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• 2010

2-Iminopyrimidines (1a-e) and 2-thioxopyrimidine (2) were synthesized using the Biginelli three component cyclocondensation reaction of an appropriate $\beta$-diketone, arylaldehyde, and guanidine (for 1a-e) or thiourea (for 2). The electrochemical properties of the novel systems were investigated by CV and DPV. Moreover, B3LYP/6-31G(d,p) method was applied to the present structures in order to gather some structural and physicochemical data.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.1031-1034
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• 2007

The R- and Z-substituent effects for the gas-phase thermal decompositions of carbamates, R2NC(=O)- OCH2CH2Z, have been investigated theoretically at B3LYP level with 6-31G(d) and 6-31++G(d,p) basis sets. Both the Z- and R-substituent effects on reactivity (ΔH≠) were well consistent with experimental results, although the R-substituent effect was underestimated theoretically. No correlations were found between activation enthalpies and reaction enthalpies. The substituent effects on reactivity seemed to be complicated at a glance, but were understandable by concurrent electronic and steric factors. Variations of bond lengths at TS structures were well correlated with the Taft's σ* values and the TS structures became tighter as the Zsubstituent became a stronger electron-acceptor (δσ* > 0). However the effects of R-substituents on the TS structures were much smaller when compared to those of Z-substituents.