• 대한화학회지
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• 제50권4호
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• pp.281-290
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• 2006

Hybrid DFT 계산 방법을 이용하여 1H-Indene과 Mono-sila-1H-indene 분자의 구조와 특성에 관한 이론적 연구를 수행하였다. 이 분자들의 방향족성 특성 연구를 위하여 MO, 비등방성 자기 민감도 등을 계산하였다. 1H-Indene과 Mono-sila-1H-indene 분자들에 대한 X8-X9 결합의 상대적인 안정도와 특성을 이해하기 위하여 NBO 계산을 수행하였다. 그 결과, 8, 9 위치의 Si 원자들이 C 원자들로 치환되었을 때, p orbital의 기여도가 증가하였다. 이러한 결과는 X8-X9 결합 길이는 하이브리드 오비탈의 p 오비탈 기여도에 크게 영향받는 사실을 보여준다. NBO계산을 통하여 X8-X9로부터 *X8-X9 결합 오비탈로의 비편재화에 기인하는 정량적인 에너지 안정화 세기를 결정하였다. MO 분석 결과 연구 대상 분자들의 방향족성은 3개의 비편재화된 pMO와 2개의 비편재화된 sMO에 의해서 주로 영향 받는다는 사실을 알 수 있었다.

• 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.

• 대한화학회지
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• 제55권3호
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• pp.392-399
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• 2011

벤조산 유도체($NH_2$, OH, H, F, Cl, CN, NO, $NO_2$) 의 두 형태를 6-311++G(d,p) 바탕 집합을 이용하여 MP2, DFT 및 HF 수준으로 연구하였으며, cis이성 질체가 더 안정하였다. 벤조산의 수소 결합 형성은 안정화 에너지를 이용하여 추산하였으며, 이합체에 대한 수소결합 에너지 계산치는 고리에서 협동 상호작용이 일어남을 보여주었다. 페닐 고리로 전자를 밀어내는 그룹(ERG)은 더 안정한 수소 결합이 형성하였다. 이합체에서 O-H 결합의 적색이동은 -565.3에서 $-589.3\;cm^{-1}$ 범위였으며, 상호 작용의 특성은 NBO 분석을 이용하여 연구하였다.

• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.201-204
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• 2002

The rates of the aminolysis of S-phenyl substituted-acetate series $(RC(=O)SC_6H_4Z$, with R=Me, Et, i-Pr, t-Bu and Bn) with benzylamines $(XC_6H_4CH_2NH_2)$ are not correlated simply with the Taft's polar $({\sigma}^{\ast})$ and/or steric effect constants $(E_s)$ of the substituents due to abnormally enhanced rate of the substrate with R=Et. Furthermore, the cross-interaction constant, ${\rho}x_z$ , is the largest with R=Et. These anomalous behaviors can only be explained by invoking the vicinal bond $({\sigma})$-antibond $({\sigma}^{\ast})$ charge transfer interaction between C-$C{\alpha}$ and C-S bonds. In the tetrahedral zwitterionic intermediate, $T^{\pm}$ , formed with R=Et the vicinal ${\sigma}_{c-c}-{\sigma}^{\ast}_{c-s}$ delocalization is the strongest with an optimum antiperiplanar arrangement and a narrow energy gap, ${\Delta}{\varepsilon}={\varepsilon}_{{\sigma}^{\ast}}-{\varepsilon}_{\sigma}$. Due to this charge transfer interaction, the stability of the intermediate increases (with the concomitant increase in the equilibrium constant K (= $k_a/k_{-a}$)) and also the leaving ability of the thiophenolate leaving group increases (and hence $k_b$ increases) so that the overall rate, $k_n\;=\;Kk_b$, is strongly enhanced. Theoretical support is provided by the natural bond orbital (NBO) analyses at the B3LYP/6-31+$G^{\ast}$ level. The anomaly exhibited by R=Et attests to the stepwise reaction mechanism in which the leaving group departure is rate limiting.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2358-2368
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• 2011

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, employing the B3LYP method and the LANL2DZ, 6-31G$^*$(LANL2DZ for Tc), 6-31G$^*$(cc-pVDZ-pp for Tc) and DGDZVP basis sets, have been performed to investigate the electronic structures and absorption spectra of the technetium-99m-labeled methylenediphosphonate ($^{99m}Tc$-MDP) complex of the simplest diphosphonate ligand. The bonding situations and natural bond orbital compositions were studied by the Mulliken population analysis (MPA) and natural bond orbital (NBO) analysis. The results indicate that the ${\sigma}$ and ${\pi}$ contributions to the Tc-O bonds are strongly polarized towards the oxygen atoms and the ionic contribution to the Tc-O bonding is larger than the covalent contribution. The electronic transitions investigated by TDDFT calculations and molecular orbital analyses show that the origin of all absorption bands is ascribed to the ligand-to-metal charge transfer (LMCT) character. The solvent effect on the electronic structures and absorption spectra has also been studied by performing DFT and TDDFT calculations at the B3LYP/6-31G$^*$(cc-pVDZ-pp for Tc) level with the integral equation formalism polarized continuum model (IEFPCM) in different media. It is found that the absorption spectra display blue shift in different extents with the increase of solvent polarity.

• Bulletin of the Korean Chemical Society
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• 제26권1호
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• pp.63-71
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• 2005

Equilibrium geometries, electronic structures, and energies of borocarbon clusters (binary compounds of carbon and boron), an unexplored class of molecules with highly unusual characteristics and potential for further development, have been investigated by means of B3LYP/6-311+G$^*$ density functional theory computations. A large number of B$_7$C${_1}^{1-}$, B$_6C_2$, and B$_5C_{3}\,^{1+}$ clusters with planar and non-planar monocyclic and polycyclic rings, as well as cage structures, have been systematically studied. Unexpectedly, planar forms are predicted not only to be the most stable structures, but also, in many cases, to have unprecedented planar heptacoordinate boron (p-heptaB) and planar heptacoordinate carbon (p-heptaC) arrangements. All these pheptaB and p-heptaC have 6π electrons and are aromatic according to the nucleus independent chemical shift (NICS). This novel bonding pattern is analyzed in terms of natural bond orbital (NBO) analysis. For virtually all possible B$_7$C${_1}^{1-}$, B$_6C_2$, and B$_5C_{3}\,^{1+}$ combinations, the p-heptaB arrangements are the more stable than other type structures.