• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4079-4083
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• 2012

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

• 대한화학회지
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• 제65권1호
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• pp.9-14
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• 2021

이 연구에서는 1기압 298 K 기체 상태에서 페난트렌에 두 개의 OH 라디칼이 연쇄적으로 작용하여 페난트렌이 분해되는 반응 과정을 B3LYP/6-31G(d,p) 기저함수를 사용하여 DFT 계산을 수행하였다. 계산 결과 두 개의 OH 라디칼이 연쇄적으로 페난트렌에 작용하는 경우에도 phenanthren-9-ol 생성 반응이 phenanthren-1-ol 생성 반응보다 유리할 것으로 예측된다. 한편 OH 첨가와 H 추출 과정에 대한 우선성은 상온에서 OH 첨가 과정이 유리할 것으로 예측되었다.

• 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 $H_2O$.

• 대한화학회지
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• 제57권4호
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• pp.461-471
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• 2013

Optimized geometrical structure, atomic charges, molecular electrostatic potential, nonlinear optical (NLO) effects and thermodynamic properties of the title compound N-(2,5-methylphenyl)salicylaldimine (I) have been investigated by using ab initio quantum chemical computational studies. Calculated results showed that the enol form of (I) is more stable than keto form. The solvent effect was investigated for obtained molecular energies, hardneses and the atomic charge distributions of (I). Natural bond orbital and frontier molecular orbital analysis of the title compound were also performed. The total molecular dipole moment (${\mu}$), linear polarizability (${\alpha}$), and first-order hyperpolarizability (${\beta}$) were calculated by B3LYP method with 6-31G(d), 6-31+G(d,p), 6-31++G(d,p), 6-311+G(d) and 6-311++G(d,p) basis sets to investigate the NLO properties of the compound (I). The standard thermodynamic functions were obtained for the title compound with the temperature ranging from 200 to 450 K.

• Bulletin of the Korean Chemical Society
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• 제25권4호
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• pp.553-556
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• 2004

In this study we have performed ab initio computer simulations to investigate the conformational characteristics of the tetraethyl (1) and triethyl ester (2) of p-tert-butylcalix[4]arene. The structures of different conformational isomers for each compound have been optimized using ab initio RHF/6-31G methods. After optimization, B3LYP/6-31+G(d,p) single point calculations of the final structures are done to include the effect of electron correlation and the basis set with diffuse function and polarization function. Relative stability of tetraethyl ester (1) of p-tert-butylcalix[4]arene is in following order: cone (most stable) > partial cone > 1,3- alternate > 1,2-alternate isomer. Relative stability of triethyl ester (2) of p-tert-butylcalix[4]arene is in following order: cone (most stable) > 2-partial cone > 1-partial cone > 3-partial cone ~ 1,3-alternate ~ 1,2- alternate isomer.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.3022-3026
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• 2013

The adsorption of carbon dioxide on graphene sheets was theoretically investigated using density functional theory (DFT) and MP2 calculations. Geometric parameters and adsorption energies were computed at various levels of theory. The $CO_2$ chemisorption energies on graphene-$C_{40}$ assuming high pressure are predicted to be 71.2-72.1 kcal/mol for the lactone systems depending on various C-O orientations at the UCAM-B3LYP level of theory. Physisorption energies of $CO_2$ on graphene were predicted to be 2.1 and 3.3 kcal/mol, respectively, at the single-point $UMP2/6-31G^{**}$ level of theory for perpendicular and parallel orientations.

• Bulletin of the Korean Chemical Society
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• 제22권4호
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• pp.395-400
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• 2001

The effects of ortho- (R = H and CH3) and Y-substituents (Y = OCH3, CH3H and CN), which are directly attached to the carbonyl carbon, on the protonation equilibria of the para-X-substituted benzoyl derivatives, 4-X -2, 6-di-R-C6H2-C(=O)-Y, are investigated theoretically using the B3LYP method with 6-31+G* basis set. Structurally, both of the (B) and (BH+ ) forms in the species with R = H are nearly coplanar regardless of the Y-substituents implying that the steric repulsion between Y-substituent and R = H is relatively small. In the species with R = CH3 , the tortional angle (Θ) between the carbonyl moiety and aryl ring varies from zero to near right angle depending on the degree of steric repulsion between Y and R = CH3 and the resonance demand. However the reaction energies, ΔG°, for the protonation processes are more favorable for R = CH3 than for R = H due to stronger electron donating effect of R = CH3 , although the species with R = CH3 are unfavorable sterically. On the other hand, the Hammett type plots are progressively better correlated with б+ than with б values on going from Y = OCH3 to Y = CN for both species with R = H and CH3 indicating that the degree of resonance delocalization between carbonyl moiety and X-substituent is increased for a more electron accepting Y-substituent. Nevertheless the effects of R = CH3 on the magnitude of Hammett type reaction constants ( б or б+ ) are not much different from those of R = H.

• 대한화학회지
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• 제63권3호
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• pp.151-159
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• 2019

본 연구는 밀도 범함수 이론(DFT) 가운데 하나인 B3LYP 방법을 $6-31G^{**}$, cc-pVDZ, cc-pVTZ의 바탕함수 집합(basis set)과 함께 사용하여 전자 공여성 분자(D)로 카바졸(carbazol) 그리고 전자 구인성 분자(A)로 dicyanobenzene, diphenyl sulfone, benzonitrile 등의 조합으로 이루어진 열 활성화 지연형광(TADF) 후보 물질에 대하여 분자구조를 최적화하고 진동주파수를 계산하였다. 또한 최적화된 분자 구조에 대하여 HOMO와 LUMO 에너지 차이를 계산하였으며, 나아가 시간 의존 밀도 범함수 이론(TD-DFT)을 사용하여 분자의 최대 흡수 및 방출 파장(${\lambda}_{max}$) 그리고 단일항과 삼중항 들뜬 상태의 에너지 차이(${\Delta}E_{ST}$) 등을 계산하여 열 활성 지연형광(TADF) 소재로서의 가능성을 예측하였다.

• Bulletin of the Korean Chemical Society
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• 제25권12호
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• pp.1911-1916
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• 2004

The conformational preference of tetrahomodioxacalix[4]arenes with three different para substituents on the phenolic ring has been investigated by using ab initio molecular orbital theory (RHF/6-31$G^{\ast}$) and density functional theory (B3LYP/6-31$G^{\ast}$). The stability order is predicted to be cone > C-1,2-alternate > partial cone > 1,3-alternate > COC-1,2-alternate. The distorted cone conformation is found to be most stable in a gas phase and the calculated results are in agreement with the reported $^1$H NMR and X-ray experimental observations. The substitution of methylene with dimethyleneoxa bridges increases the size of the annulus of the molecule, its conformational mobility, and the number of hydrogen bonding patterns. The thermodynamic stability and the conformational characteristics of tetrahomodioxacalix[4]arenes are discussed in regards of the number of phenolic hydrogen bonding patterns and the polarity of a molecule. The substituent effects on the para position of the phenolic ring are also introduced.

• 대한화학회지
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• 제42권6호
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• pp.629-637
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• 1998

$6-31+G^{\ast}^{\ast}와\;6-311+G^{\ast}^{\ast}$의 기본조를 사용해서 이합체 분자착물 FH…FH, FH…CO, FH…OC 뿐만 아니라 $(HF)_2(CO)$의 형성가능한 두가지 삼합체 분자착물들에 대해서 HF-SCF, MP2 그리고 B3LYP 계산을 수행했다. 이 삼합체 분자착물들에 대한 여러 가지 바닥상태 성질들을 구하였으며, 대응하는 단위체들과 이합체들의 성질들과 비교하였다. FH…CO가 FH…OC에 비해 평균 0.85 kcal/mol 만큼 안정했고, F-H…F-H…C≡O가 F-H…F-H…O≡C 보다 1∼2 kcal/mol 만큼 안정한 것으로 계산되었다. 삼합체 분자착물 형성에 따른 C≡O stretching band 는 그들의 이합체들(FH…CO, FH…OC)에 비해 각각 24, $37\;cm^{-1}$만큼, H-F stretching band는 각각 $54, 353\; cm^{-1}$만큼 red shift 되는 것으로 평가되었다.