• Bulletin of the Korean Chemical Society
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• v.24 no.6
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• pp.792-796
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• 2003

Polychlorinated dibenzo-p-dioxins (PCDDs) are extremely toxic and persistent environmental pollutants. Their chemical reactivities and other physicochemical/biological properties show a strong dependence on the chlorination pattern. With increasing the number of chlorines, dioxin congeners become more electronegative and gain higher electron affinities. The vertical electron affinities (VEA) are related with the LUMO energies of neutral molecules. LUMO energies of all PCDD congeners were calculated at the B3LYP/6-31G** level and those of some selected congeners at the level of B3LYP/6-311G**//B3LYP/6-31G** and B3LYP/cc-pvtz/ /B3LYP/6-31G**. The total energies of neutral and anionic species for dibenzo-p-dioxins (DD), 1469-TCDD, 2378-TCDD, and OCDD were calculated at the level of B3LYP/6-31G**, B3LYP/aug-cc-pvdz, and B3LYP/ aug-cc-pvtz//B3LYP/6-31G**. By using the four congeners with D2h symmetry as reference molecules, we could estimate VEA (B3LYP/aug-cc-pvdz) of 75 PCDD congeners based on the linear correlations between LUMO energy and VEA (B3LYP/6-31G**) and between VEA (B3LYP/6-31G**) and VEA (B3LYP/aug-ccpvtz// B3LYP/6-31G**). Results show that all PCDDs with the number of Cl ≥ 3 have positive electron affinities. The PCDD electron affinity values provided in this work can be a useful data set in understanding the congener-specific reactivities of dioxins in various environmental media.

• Journal of the Korean Applied Science and Technology
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• v.39 no.4
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• pp.535-541
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• 2022

The radical reaction position was calculated by varying the calculation level for ACEL and ANT, which are detected with the highest frequency and concentration in PAHs pollution sites. The results of each calculation level were compared and evaluated with the existing literature. HF, B3LYP, B3LYP-D, and MP2 were used as the method for each level used for calculation. Except for HF, the MK charge by B3LYP, B3LYP-D, and MP2 was consistent with the experimental results. It was found that the dispersion effect was negligible in the calculation of ACEL and ANT because the calculation results by the B3LYP and B3LYP-D methods were the same. In particular, it was found that the MK charge calculation result by MP2 agrees well with the product/PAH ratio obtained as a result of the experiment. Considering the calculation cost, it would be preferable to use B3LYP to predict the radical reaction site of ACEL and ANT. However, considering the product/PAH ratio, it takes more time to calculate, but it is judged that it is better to use the MP2.

• Bulletin of the Korean Chemical Society
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• v.17 no.8
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• pp.760-764
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• 1996

The molecular geometry and vibrational frequencies of 9-fluorenone have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr(B3LYP) density functional methods with 6-31G* basis set. Harmonic vibrational frequencies obtained from the B3LYP calculation show good agreement with the available experimental data. A few vibrational fundamentals are newly assigned based on the B3LYP results. The B3LYP calculation is reconfirmed to be useful in the assignment of the fundamental vibrational frequencies.

• Bulletin of the Korean Chemical Society
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• v.19 no.1
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• pp.93-98
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• 1998

The molecular geometries and harmonic vibrational frequencies of biphenyl in the ground and the first excited triplet states have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr (B3LYP) density functional methods with 6-31G* basis set. Structural change occurs from a twisted benzene-like to a planar quinone-like form upon the excitation to the first excited state. Scaled harmonic vibrational frequencies for the ground state obtained from the B3LYP calculation show good agreement with the available experimental data. A few vibrational fundamentals for both states are newly assigned based on the B3LYP results.

• Bulletin of the Korean Chemical Society
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• v.29 no.7
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• pp.1374-1378
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• 2008

Using DFT B3LYP/6-31+G(d,p)//B3LYP/6-31G(d,p) calculation method, stable molecular structures were optimized for the p-tert-butylcalix[4]arene functionalized at lower rim by cage-annulated crown ether (1) in two different conformers and their potassium-ion complexes. Cone conformer of free host 1 was slightly more stable than partial-cone conformer. For two different kinds of complexation mode, the potassium ion in benzene-rings (bz) pocket showed comparable complexation efficiency with the cation in cage-annulated crown-ether (cr) for the cone and partial-cone conformers of 1. The complex (1${\bullet}K^+$) in the cr-binding mode for the partial-cone conformer was more stable than the cone conformer for B3LYP/6-31G(d,p) geometry optimization. However, $1_{(cone)}{\bullet}K^+$(cr) showed lower single-point energy than the $1_{(pc)}{\bullet}K^+$(cr) for B3LYP/6- 31+G(d,p) calculation method.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3514-3520
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• 2014

Molecular structures of the various conformers of para-bromocalix[4]aryl derivatives 1-4 were optimized using the DFT B3LYP calculation method. The total electronic and Gibbs free energies and normal vibrational frequencies of the different structures (CONE, partial cone (PACO), 1,2-Alternate(1,2-A) and 1,3-Alternate(1,3-A)) were calculated from the four kinds of para-bromocalix[4]aryl derivatives. The B3LYP/6-31G(d,p) calculations suggested the following: 1(PACO) is the most stable among four conformers of 1; 2(CONE) is the most stable among five conformers of 2; 3(PACO) is the most stable among four conformers of 3; 4(1,3-A) is the most stable among four conformers of 4. All the most stable structures optimized by the B3LYP calculation method were in accordance with the experimental crystal structures of 1-4. The calculated IR spectra of the various conformers (CONE, PACO, 1,2-A and 1,3-A) of 1-4 were compared.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.847-851
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• 2004

The complexation characteristics of tetramethyl (1) and tetraethyl esters (2) of p-tert-butylcalix[4]arene with alkali metal cations have been investigated by ab initio calculation. The structures of endo- or exocomplexation of the hosts in cone conformation with alkali metal ions have been optimized using HF/6-31G method followed by B3LYP/6-31G(d) single point calculation. B3LYP/6-31G(d) calculations suggest that exo-complexation efficiencies of sodium ion to the cavity of lower rim of hosts 1 and 2 are 27.1 and 25.8 kcal/mol better than that of potassium ion, respectively. The exo-complexation efficiencies of potassium ion to the cavity of lower rim of hosts 1 and 2 are 33.3 and 31.5 kcal/mol better than the endo-complexation inside the upper rim (four aromatic rings) as expected from the experimental results. B3LYP/6-31G(d) calculation of the ethyl ester 2 shows 29.5 and 30.8 kcal/mol better exo-complexation efficiency for both sodium and potassium ions than the methyl ester 1.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.90-96
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• 2004

The conformations of dicyclopropyl, isopropyl cyclopropyl, and diisopropylcarbenes were optimized using density functional theory (B3LYP/6-31G(d)). We showed that the optimized geometries of carbenes with cyclopropyl groups are fully in accord with those expected for bisected W-shaped conformations, in which the effective hyperconjugation of a cyclopropyl group with singlet carbene can occur. The stabilization energies were evaluated at the B3LYP/6-311+G(3df, 2p)//B3LYP/6-31G(d) + ZPE level using an isodesmic equation. The relative stability of carbenes is in the order $(c-Pr)_2$C: > (i-Pr)(c-Pr)C: > $(i-Pr)_2$C:, and a cyclopropyl group stabilizes carbene more than an isopropyl group by nearly 9 kcal/mol. Energies for the decomposition of diazo compounds to carbenes increase in the order $(c-Pr)_2$ < (i-Pr)(c-Pr) < $(i-Pr)_2$ by ~9 kcal/mol each. From a singlettriplet energy gap ($E_{ST}$) calculation, the singlet level is lower than the triplet level and the $E_{ST}$ shows a trend similar to the stabilization energy calculations. For comparison, the optimized geometries and stabilization energies for the corresponding carbocations were also studied at the same level of calculation. The greater changes in geometries and the higher stabilization energies for carbocations compared to carbenes can explain the greater hyperconjugation effect.

• Bulletin of the Korean Chemical Society
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• v.22 no.6
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• pp.605-610
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• 2001

The molecular geometries and harmonic vibrational frequencies of dibenzofuran in the ground and lowest triplet state have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr(B3LYP)density functional methods with the 6-31G basis set. Upon the excitation to the lowest triplet state, the molecular structure retains the planar form but distorts from a benzene-like to a quinone-like form in skeleton. Scaled vibrational frequencies for the ground and lowest triplet state obtained from the B3LYP calculation show excellent agreement with the available experimental data. A few vibrational fundamentals for both states are newly assigned based on the B3LYP results.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1855-1858
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• 2004

Molecular geometries for the cationic and neutral species of OXO (X=Cl, Br, and I) are optimized using the Hartree-Fock (HF) theory, the second order Moller-Plesset perturbation theory (MP2), the density functional theory with the B3LYP hybrid functional (B3LYP), and the coupled cluster theory using single and double excitation with a perturbational treatment of triplet excitation (CCSD[T]) methods, with two basis sets of triple zeta plus polarization quality. The single point calculations for these species are performed at the CCSD(T,Full) level. The harmonic vibrational frequencies for these species are calculated at the HF, MP2, B3LYP and CCSD(T) levels. The adiabatic ionization potential for OIO is calculated to be 936.7 kJ/mol at the CCSD(T,Full) level and the correct value is estimated to be around 945.4 kJ/mol.