• Bulletin of the Korean Chemical Society
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• 제30권5호
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• pp.1061-1066
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• 2009

Two fluoro-substituted 2-pyrazoline derivatives, 1-phenyl-3-(4-methoxyphenyl)-5-(4-fluorophenyl)-2-pyrazoline (1) and 1-phenyl-3-(4-methoxyphenyl)-5-(2-fluoro-phenyl)-2-pyrazoline (2) have been synthesized and characterized by elemental analysis, IR, UV-Vis and fluorescence spectra. The crystal structure of 1 has been determined by X-ray single crystal diffraction. For the two compounds, density functional theory (DFT) calculations of the structures and natural population atomic charge analysis (NPA) have been performed at B3LYP/6-311G** level of theory. By using TD-DFT method, electron spectra of 1 and 2 have been predicted, which are very approximate with the experimental ones. Comparative studies on 1 and 2 indicate that the location change of fluorine atom in 5-position phenyl ring of 2-pyrazoline does not make significant change of geometries and electronic transition bands, but it leads to evident change of atomic charge distributions and peak intensities of UV and fluorescence spectra.

• EDISON SW 활용 경진대회 논문집
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• 제4회(2015년)
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• pp.6-13
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• 2015

이 연구는 초기 지구의 대기 환경에서 유기화합물(glycine)이 합성되는 실험(Urey-Miller 실험)에서의 반응 경로를 Deterministic한 방법의 중간체 sampling 방법으로 반응 네트워크를 구성하고 Yen's알고리즘으로 네트워크 내의 최단경로를 제시함으로써 반응물과 생성물이 결정되어 있을 때 최소한의 화학적 직관만을 이용하여 제시하는 것이 목표이다. 이 연구 결과는 2014년도 Nature Chemistry에 발표된 다른 방법론을 적용하여 제시된 Urey-Miller reaction path와 비교해 어떠한 반응이 상대적으로 더 타당한 경로를 제시했을지 알아보았다. 이 연구에서 나온 reaction path에서의 중간체들에 대해 GAMESS를 이용한 B3LYP/6-31g(d,p) DFT계산을 수행하였다. 결과를 분석해보면서 어떤 부분이 부족하며 이 연구에 적용한 방법론을 어떻게 발전시켜나가야 더 나은 결과를 얻을 수 있을지를 함께 고려해 보았다.

• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3265-3268
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• 2013

The multi-hydrogen bonded systems with the solvated electrons are investigated at the B3LYP/6-311++$G^{**}$ basis set level. The symmetrical linear geometrical characteristic is common for the dimer systems, while for the tetramer system, the tetrahedron configuration is generated. The NBO charge analyses demonstrate that the multi-hydrogen-multi-electron (mH-ne) coupling exist in these anion systems, as is supported by the electrostatic potential and the molecular orbital analyses. The positive chemical shift value of the central hydrogen ($H_c$) and the negative chemical shift value of the terminal hydrogen ($H_t$) indicate that the $H_c$ is electronegative while the $H_t$ is electropositive, respectively. Strong coupling between two central hydrogen atoms is demonstrated by the large spin-spin coupling constants. The solvated electron donates significant contributions for the stability of these systems.

• 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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• 제27권7호
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• pp.1048-1052
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• 2006

Ab initio calculations of the structure, atomic charges and natural bond orbital (NBO) have been performed at HF/6-311G** and B3LYP/6-311G** levels for the title compound of dibenzothiazyl-disulfide. The calculated results show that the two nitrogen atoms have the biggest negative charges and they are the potential sites to react with the metallic ions, which make the title compound become a di-dentate ligand. Vibrational frequencies of the title compound have been obtained and compared with the experimental value and the comparison indicates that B3LYP/6-311G** level is better than HF/6-311G** level to predict the vibrational frequencies for the system studied here. For the title compound, electronic absorption spectra calculated by time?ependent density functional theory (TD-DFT) are more accurate than Hartree-Focksingle-excitation CI (CI-Singles) method. NBO analyses show that the electronic transitions are mainly derived from the contribution of bands $\pi\rightarrow\pi^{*}$. Thermodynamic calculated results show that the formation of the title compound from 2-mercaptobenzothiazole is a spontaneous process at room temperature with the change of free Gibbs being negative value.

• 대한화학회지
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• 제53권6호
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• pp.671-676
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• 2009

밀도 함수이론을 사용해 철 부식 방지제로써 메톨(N-메틸-p-아미노페놀 설페이트)에 대한 기하학적 및 전자구조에 대한 연구가 처음으로 기술되었다. B3LYP/6-31G+(d,p) 기저세트를 사용해 기상 및 액상에서 HOMO, LUMO, 에너지갭 (${\Delta}E$), 멀리칸하전 ($q_M$), 자연원자하전 ($q_n$)과 같은 양자화학적 변수들이 계산되었다. 부식방지메카니즘을 이해하기 위해 부식방지효율과 양자화학적 변수들간의 연관성이 논의되었다.

• 대한화학회지
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• 제53권5호
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• pp.512-520
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• 2009

본 연구에서는 반응성이 큰 황이 산소와 결합하여 산화황이 되고 이것들이 클러스터를 이루었 을 때의 구조와 결합에너지에 대하여 조사하였다. $S_{n}O_{n},\;S_{n}O_{2n},\;S_{n}O_{3n}\;(n\;=\;1{\sim}4)$까지의 여러 가능한 분자 구조를 B3LYP/6-311G** 이론수준까지 최적화 하였으며, 단량체($SO,\;SO_2,\;SO_3$)가 증가할 때의 결합에너지를 MP2/6-311G** 수준까지 계산하였다. $SnOn\;(n\;=\;1{\sim}4)$의 경우 S-O 단량체 증가에 따라 상대적으로 안정화되는 경향이 강하게 나타났으며, 약 20-25 kcal/mol 정도 증가하는 것으로 예측 되었다. 반면 $S_nO_{2n},\;S_nO_{3n} \;(n\;=\;1{\sim}4)$의 경우에는 $SO_2$ 나 $SO_3$ 의 증가에 따른 열역학적 안정성이 상대적으로 덜 안정화 되는 것으로 나타났으며, SO2 단량체가 증가함에 따른 결합에너지 변화는 2.2 kcal/mol, 그리고 $SO_3$ 단량체가 증가함에 따라 흡열반응으로 나타나 열역학적으로 더욱 불안정해질 것으로 예상된다.

• 대한화학회지
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• 제59권2호
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• pp.117-124
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• 2015

Hydrogen polyoxide, $H_2O_n-H_2O_m$(n=1-4, m=1-4) 이중합체(dimer)의 분자 구조 변화에 따른 수소결합(H-bonding) 효과를 순 이론적(ab initio) 방법과 밀도 범함수 이론(DFT)으로 계산하였다. 분자 구조는 B3LYP, CAM-B3LYP, MP2의 양자역학적 방법들을 사용하여 최적화하였으며, 진동주파수를 계산하여 최저에너지(true local minimum) 구조인 것을 확인하였다. 보다 정확한 수소결합 에너지(${\Delta}E$) 계산을 위하여 CCSD(T) 이론수준에서 한 점(single-point) 에너지 계산을 하였으며, 영점 진동에너지(ZPVE) 보정과 바탕집합 중첩에러(BSSE) 보정을 하였다. CCSD(T)/cc-pVTZ 이론 수준에서 $H_2O_4-H_2O_3$이 8.18 kcal/mol로 가장 강한 결합을 나타내었으며, 물 이중합체($H_2O-H_2O$)는 3.00 kcal/mol로 가장 약한 결합에너지를 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.409-414
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• 2009

Novel binol aldehydes derivatized at 2' hydroxy position with both uryl and acetamide groups (2), and diuryl groups (3) have been synthesized. Both were designed for streospecific binding and chirality conversion of general dipeptides with support of multiple hydrogen bonding donor sites in the receptors. The receptors, 2 and 3, converted the chirality of N-terminal amino acids of peptides such as Ala-Gly, Met-Gly, Leu-Gly and His-Gly with stereoselectivity on D-form over L-form. The stereoselectivity ratios were in the range of 5-11, somewhat higher than those of the binol receptor with mono uryl group (1). The DFT calculation at the B3LYP/6-31G$^*$//MPWB1K/6-31G$^*$ level revealed that 3-D-Ala-Gly was 2.2 kcal/mol more stable than 3-L-Ala-Gly. The considerable steric hindrance between the methyl group of the alanine and the imine CH moiety of the receptor seems to be the main contributing factor for the thermodynamic preference.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2897-2902
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• 2010

Seven fully optimized geometries of 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) dimers have been obtained with density functional theory (DFT) method at the B3LYP/$6-311++G^{**}$ level. The intermolecular interaction energy was calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction energy of the dimers is $-23.69\;kJ{\cdot}mol^{-1}$. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. Based on the vibrational analysis, the changes of thermodynamic properties from the monomers to dimer with the temperature ranging from 200.0 K to 800.0 K have been obtained using the statistical thermodynamic method. It was found that the hydrogen bonds dominantly contribute to the dimers, while the binding energies are not only determined by hydrogen bonding. The dimerization process can not occur spontaneously at given temperatures.