• Journal of Photoscience
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• v.7 no.2
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• pp.67-71
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• 2000

A quantum-chemical investigation on the conformations and electronic properties of trans(diphenyl-diheterocyclic) ethenes(t-PHEs) as building block for fully $\pi$-conjuated polymer are performed in order to display the effects of heterocyclic ring substitution. Structures for the molecules, t-PHEs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF methods, with 6-31G basic set. The potential energy curves with respect to the change of single are obtained by using ab initio HF/6-31G basic set. The curves are not similar shapes in the molecules with respect to heterocyclic rings. It is shown that the steric repulsion interactions between phenyl ring and heterocyclic ring are subjected to different type with the respect to each heterocyclic ring. Electronic properties of the molecules were molecules were obtained by applying the optimized structures and selected geometries to the extended Huckel method. To investigate the change of HOMO-LUMO gap with respedt to the torsion angle, we select the optimized structures. By using the results, the dependency of conjugation for the energy gaps is analyzed. For t-PHE the energy gap increase up to 0.52 eV compared with its planar structure. In the cases of t-PHE and t-PHE, the energy gap increase by 1.29 and 1.15 eV, respectively, compared with its planar structure.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.120.2-120.2
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• 2011

The improvement of solar energy-to-electricity conversion efficiency has continued to be an important research area of dye-sensitized solar cells (DSSCs). The mechanism of DSSCs is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2 or ZnO. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO band gaps of dye moleculed in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. Organic dyes, because of their many advantages, such as high molar extinction coefficients, convenience of customized molecular design for desired photophysical and photochemical properties, inexpensiveness with no transition metals contained, and environment-friendliness, are suitable as photosensitizers for DSSC. We believe that practically useful organic dye photosensitizers can be produced by exploiting electron donor/acceptor system with proper length of ${\pi}$-conjugation in a chromophore to control the absorption wavelength and enhance the photovoltaic performance. In this research, We designed and synthesized organic dyes also investigated the photoelectrochemical properties of a series of ionic dyes in DSSCs.

• Journal of the Korean Chemical Society
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• v.27 no.6
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• pp.391-398
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• 1983

The reaction for the hydrogen abstraction from substituted-toluenes by t-butoxyl and t-butyl radical have been studied MO theoretically using CNDO/2 method. The reaction for the abstraction from substituted-toluenes by t-butoxyl radical showed the negative ${\rho}$ values from Hammett equation, since t-butoxyl radial is electrophilic, relatively low energy SOMO, which can interact with HOMO energy of substituted-toluens. On the other hand, t-butyl radical is nucleophilic, relatively high energy SOMO, which can interact with LUMO energy of substituted-toluenes. And so the reaction of abstraction from substituted-toluenes by t-butyl radical exhibited positive ${\rho}$ values.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.473-473
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• 2012

유기발광소자는 낮은 구동전압, 빠른 응답속도, 넓은 시야각 등의 장점으로 소형 디스플레이에 사용되며 차세대 조명으로 관심을 받고 있다. 고효율의 유기발광소자를 제작하기 위해서 다양한 유기 인광물질 합성 및 연구가 진행되고 있으며, 다양한 호스트 물질을 사용하여 전자와 정공의 주입을 향상하여 고효율의 인광 유기발광소자를 제작하였다. 본 논문에서는 발광층에 N,N'-dicarbazolyl-3,5-benzene (mCP)와 1,3,5-tri(phenyl-2-benzimidazole)-benzene (TPBi)를 혼합 호스트로 사용하였으며 tris(2-phenylpyridine)iridium ($Ir(ppy)_3$)청색 인광물질을 도핑하여 고효율의 인광 유기발광소자를 제작하였다. 유기발광소자의 발광층에 단일 호스트와 혼합 호스트의 전기적 및 광학적 특성을 비교 분석하여 전자 및 정공 수송 메커니즘을 규명하였다. 혼합 호스트 TPBi의 lowest unoccupied molecular orbital (LUMO) 준위와 엑시톤 저지층 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)의 LUMO 준위와 비슷하여 전자의 주입을 향상시키는 역할을 하며, 다른 혼합 호스트 mCP는 highest occupied molecular orbital (HOMO)와 정공수송층 N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB)의 HOMO와 비슷하여 정공의 주입을 향상시키는 역할을 하여, $Ir(ppy)_3$에 전자와 정공의 주입이 향상되어 고 효율의 인광 유기발광소자를 제작할 수 있었다. 이와 같은 실험결과는 인광 유기발광소자의 호스트 물질에 따른 전하주입 메커니즘을 설명 하였으며 고효율의 인광 유기발광소자 제작에 도움을 줄 것이다.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3211-3217
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• 2013

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of three D-${\pi}$-A-type organic dyes (C1-1, D5 and TH208) containing identical ${\pi}$-spacers and electron acceptors, but different aromatic amine electron-donating groups (tetrahydroquinoline, triphenylamine and phenothiazine). The coplanar geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating ability of tetrahydroquinoline is stronger than those of triphenylamine and phenothiazine. The computed orbital energy levels of these dyes confirm that the electrons could be injected from the excited dyes to the semiconductor conduction band and the oxidized dyes could be reduced effectively by electrolyte. The TD-DFT results show that the CAM-B3LYP/6-31+G(d, p) is suitable for calculating the absorption spectra. The first absorption band for these dyes is assigned to the HOMO${\rightarrow}$LUMO and HOMO-1${\rightarrow}$LUMO transitions.

• Journal of the Korean Chemical Society
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• v.40 no.2
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• pp.122-127
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• 1996

The PPP-MO method has been used to calculate the $\pi$ electronic excitation energy of fluorane dyes. A good correlation between the absorbed and calculated values for the ${\pi}{\rightarrow}\pi*$ transition was found for fluorane dyes. The effect of substituents on the color of fluorane dye was studied on the basis of these calculated results, i.e. HOMO-LUMO energy levels and $\pi-electron-density$ changes accompanying the first excitation.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.279-283
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• 1984

${\beta}$-Substituent effect on the reactivity of retro-ene decarboxylation of but-3-enoic acid was investigated theoretically. It was found that charge effect is important not only through ${\pi}$-electron transfer as has been claimed to rationalize experimental results but also through polarization as found for the $CH_3$ substituent. The reactivity was not determined by the charge effect alone but the HOMO-LUMO energy gap was also found to affect the reactivity. In general it was confirmed that the greater the ${\pi}$-electron donating power of the substituent, the greater is the reactivity.

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.7-17
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• 1982

In order to predict substituent and Lewis acid effects on the regiospecificity of the Diels-Alder reaction, and to investigate the competition for the complexation of Lewis acid between diene and dienophile, frontier orbital theory has been applied to thermal and catalyzed Diels-Alder reaction by means of CNDO/2 MO method. It has been found that: (1) Lewis acid coordinated preferentially with diene rather than dienophile when carbonyl oxygen of acetoxy substituted diene had larger negative atomic charges than that of dienophile. (2) Most of the reaction were neutral electron demand type, and hence 4-C, 2-C and quantitative secondary orbital interacion methods were generally in good accord with experiments. (3) Sulfur activated the adjacent terminal carbon atom greatly to increase diene LUMO-dienophile HOMO interaction through vacant-d-orbital participation, and played an important role in controlling regioselectivity of neutral electron demand reaction type.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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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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• v.34 no.7
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• pp.2093-2098
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• 2013

Density functional theory (DFT) was used to determine the ground state geometries of indigo and new design dyes (IM-Dye-1 IM-Dye-2 and IM-Dye-3). The time dependant density functional theory (TDDFT) was used to calculate the excitation energies. All the calculations were performed in both gas and solvent phase. The LUMO energies of all the dyes were above the conduction band of $TiO_2$, while the HOMOs were below the redox couple (except IM-Dye-3). The HOMO-LUMO energy gaps of new design dyes were smaller as compared to indigo. All new design dyes were strongly red shifted as compared to indigo. The improved light harvesting efficiency (LHE) and free energy change of electron injection ${\Delta}G^{inject}$ of new designed sensitizers revealed that these materials would be excellent sensitizers. The broken coplanarity between the benzene near anchoring group having LUMO and the last benzene attached to TPA unit in all new design dyes consequently would hamper the recombination reaction. This theoretical designing will the pave way for experimentalists to synthesize the efficient sensitizers for solar cells.