• Bulletin of the Korean Chemical Society
• /
• 제28권2호
• /
• pp.241-245
• /
• 2007

The electronic structures of the new organic conducting salts, the β'- and β''-phases of (BEDT-TTF)2[(IBr2)0.2(BrICl)0.1(ICl2)0.7], were examined by calculating their electronic band structures, Fermi surfaces and HOMO-HOMO interaction energies using the extended Huckel tight binding method. On the basis of these calculations, we probed why the β'-phase is semiconducting while the β ''-phase is metallic.

• 한국염색가공학회지
• /
• 제25권3호
• /
• pp.159-164
• /
• 2013

Pyrene based molecule has been synthesized through the reaction of pyrene-1-carboxaldehyde and 4- phenylthiosemicarbazide in this research. The pyrene based molecule showed specific optical properties such as absorption and emission changes after mixing with fluoride in DMSO. The phenomenon is induced by the interaction of the molecule and fluoride. This interaction may affect to electron distributions and potential energy levels. In this regard, synthesized pyrene based molecule has been investigated for its electron distributions and HOMO/LUMO energy levels depending on interaction with fluoride. The absorption measurement, cyclicvoltammograms and computational method were investigated to calculate and compare energy potential levels.

• 한국진공학회지
• /
• 제17권5호
• /
• pp.394-399
• /
• 2008

산화규소막에 Octadecyltrichlorosilane (OTS)로 자기조립층을 형성하기 전후에 펜타신을 흡착하여 광전자분광기술 및 광전현미경을 이용하여 전자구조 및 분자성장을 비교 관찰하였다. OTS처리한 경우 펜타신과 기판사이의 상호작용이 비교적 약하여 펜타신의 표면 확산이 활발하고 펜타신끼리 서로 뭉쳐서 성장함으로써, 시료와 펜타신의 에너지준위 정렬을 나타내는 HOMO 오프셋 값이 계속적으로 변하는 결과를 가져온다. 이에 반해 산화규소막 위에서는 펜타신이 기판과 비교적 강하게 결합하여 초기부터 에너지준위 정렬값에 크게 기여를 하고 두께가 증가해도 그 변화는 미미하다.

• 한국정보디스플레이학회:학술대회논문집
• /
• 한국정보디스플레이학회 2009년도 9th International Meeting on Information Display
• /
• pp.108-111
• /
• 2009

We have determined the electronic energy level alignment at the interface between 4,4'-bis-N-phenyl-1-naphthylamino biphenyl (NPB) and 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile (HAT-CN) using ultraviolet photoelectron spectroscopy (UPS). The highest occupied molecular orbital (HOMO) of 20 nm thick HAT-CN film was located at 3.8 eV below the Fermi level. Thus the lowest unoccupied molecular orbital (LUMO) is very close to the Fermi level. The HOMO position of NPB was only about 0.3 eV below Fermi level at NPB/HAT-CN interface. This enables an easy excitation of electrons from the NPB HOMO to the HAT-CN LUMO, creating electron-hole pairs across this organic-organic interface. We also study the interaction of HAT-CN with a few metallic surfaces including Ca, Cu, and ITO using UPS and ab-inito electronic structure calculation techniques.

• Journal of Microbiology and Biotechnology
• /
• 제17권11호
• /
• pp.1789-1796
• /
• 2007

A ${\beta}$-glucosidase with the molecular mass of 160,000 Da was purified to homogeneity from cell extract of a cellulolytic bacterium, Cellulomonas uda CS1-1. The kinetic parameters ($K_m$ and $V_{max}$) of the enzyme were determined with pNP-cellooligosccharides (DP 1-5) and cellobiose. The molecular orbital theoretical studies on the cellulolytic reactivity between the pNP-cellooligosaccharides as substrate (S) molecules and the purified ${\beta}$-glucosidase (E) were conducted by applying the frontier molecular orbital (FMO) interaction theory. The results of the FMO interaction between E and S molecules verified that the first stage of the reaction was induced by exocyclic cleavage, which occurred in an electrophilic reaction based on a strong charge-controlled reaction between the highest occupied molecular orbital (HOMO) energy of the S molecule and the lowest occupied molecular orbital (LUMO) energy of the hydronium ion ($H_3O^+$), more than endocyclic cleavage, whereas a nucleophilic substitution reaction was induced by an orbital-controlled reaction between the LUMO energy of the oxonium ion ($SH^+$) protonated to the S molecule and the HOMO energy of the $H_2O_2$ molecule. A hypothetic reaction route was proposed with the experimental results in which the enzymatic acid-catalyst hydrolysis reaction of E and S molecules would be progressed via $SN_1$ and $SN_2$ reactions. In addition, the quantitative structure-activity relationships (QSARs) between these kinetic parameters showed that $K_m$ has a significant correlation with hydrophobicity (logP), and specific activity has with dipole moment, respectively.

• 농약과학회지
• /
• 제2권3호
• /
• pp.64-69
• /
• 1998

기질(S) 화합물로 30종의 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide 유도체들을 합성하고 벼 잎집무늬 마름병균(Rhizoctonia solani)과 밀 붉은 녹병균(Puccinia recondita)에 대한 항균활성(in vivo) 값($pI_{50}$)을 측정하였다. (S)는 잘록병균보다 밀 붉은녹병균에 대하여 보다 큰 항균활성을 나타내었으며 두 종의 균에 대하여 3-methoxy, 11, 3-iso-propyloxy, 13 및 3-iso-propyl 치환체, 25가 제일 큰 활성을 보였다. 그리고 치환(X)-phenylcarbamoyl group의 변화에 따른 물리-화학 파라미터와 항균활성($pI_{50}$)으로부터 구조-활성관계(SAR)를 검토 한 결과, 벼 잎집무늬 마름병균에 대하여는 공명효과에 따른 전자밀게(R<0)의 소수성이 큰(${\pi}>0$) m-alkyl 치환기(X)가, 그리고 밀 붉은녹병균에 대하여는 분자 분극율(Sp.Pol.)과 분자의 음하전(ABSQ<0)을 위시하여 HOMO에너지(e.v.)가 클수록(HOMO<0) 높은 항균활성을 나타내었다. 또한, 전하-조절 반응에 의한 수용체-(S)간의 상호작용과 높은 활성발현 조건들이 검토되었다.

• Bulletin of the Korean Chemical Society
• /
• 제15권8호
• /
• pp.658-662
• /
• 1994

Ab initio and extended Huckel calculations have been applied to discuss the electronic structure, ring inversion barrier, and geometry of the $Cp_2TiS_3$ compound. The deformation of four membered ring in the planar geometry is originated from a second-order Jahn-Teller distortion due to the small energy gap between HOMO and LUMO on the basis of extended Huckel calculations. The puckered $C_s$ geometry is stabilized by the interaction of the $x^2-y^2$ metal orbital with the hybrid orbital in sulfur. Ab initio calculations have been carried out to explore the ring inversion process for the model $Cl_2TiS_3$ compound. We have optimized $C_s$ and $C_{2v}$ structures of the model compound at the RHF level. The energy barriers for the ring inversion are sensitive to the used basis set. With 4-31$G^*$ for the Cl and S ligands, the barriers are computed to be 8.41 kcal/mol at MP2 and 8.02 kcal/mol at MP4 level.

• Bulletin of the Korean Chemical Society
• /
• 제30권1호
• /
• pp.205-213
• /
• 2009

This study reports on the geometry optimizations and electronic structure calculations for methyl pyropheophorbide (MPPa), tropolonyl methyl pyropheophorbides (TMPPa, ITMPPa), and cationic tropolonyl methyl pyropheophorbides ($TMPPa^+{{\cdot}BF_4}^-,\;ITMPPa^+{{\cdot}BF_4}^-,\;TMPPa^+,\;and\;ITMPPa^+$) using Local Spin Density Approximation (LSDA/ 6-31G*) and the Restricted Hatree-Fock (RHF/6-31G*) level theory. From the calculated results, we found that substituted cationic tropolonyl groups have larger structural effects than those of substituted neutral tropolonyl groups. The order of structural change effects is $ITMPPa^+ > ITMPPa^+{{\cdot}BF_4}^-$ > ITMPPa, as a result of the isopropyl group. Because it is an electron-releasing group, the substituted isopropyl group electronic effect on a 3-position tropolone increases the Highest Occupied Molecular Orbital and Lowest Unoccupied Molecular Orbital (HOMO-LUMO) energy gap. It was constituted that the larger the cationic characters of these photosensitizers, the smaller the HOMOLUMO band gaps are. The orbital energies of the cationic systems and the ions are stronger than those of a neutral system because of a strong electrostatic interaction. However, this stabilization of orbital energies are counteracted by the distortion of chlorin macrocycle, which results in a large destabilization of chlorin-based compound HOMOs and smaller destabilization of LUMOs as shown in TMPPa (ITMPPa), $TMPPa^+{{\cdot}BF_4}^- (ITMPPa^+{{\cdot}BF_4}^-),\;and\;TMPPa^+\;(ITMPPa^+)$ of Figure 6 and Table 6-7. These results are in reasonable agreement with normal-coordinate structural decomposition (NSD) results. The HOMO-LUMO gap is an important factor to consider in the development of photodynamic therapy (PDT).

• Bulletin of the Korean Chemical Society
• /
• 제23권6호
• /
• pp.807-811
• /
• 2002

We present a hypothetical quantum scattering model to propose a novel electroluminescence device. Adoping with features of solid state semiconductor LED and exciplex laser, the cathode (electrol incoming potential) and anode(electron outgoing potential) are made to correspond to two 1-dimensional resonance supporting potentials, and the light emitting part to an interaction potential in the intermediate region. When an external voltage is applied, the electron flows into the cathode having small work function. Subsequently in flows via LUMO of the " electron incoming potential" loses kinetic energy emitting a photon, then continues to flow via LUMO of the "electron outgoing potential" unlike the conventional LUMO to HOMO transitions occurring in solid state semiconductor LED. In this model, the photon frequency can be controlled by adijusting the applied voltage. The model hopefully could be realized as partially conjugated hydrocarbon chains.

• Bulletin of the Korean Chemical Society
• /
• 제23권2호
• /
• pp.330-336
• /
• 2002

A quantum-chemical investigation on the conformations and electronic properties of bis[2-{2-methoxy-4,6-di(t-butyl)phenyl}ethenyl]benzenes (MBPBs) as building block for ${\pi}$-conjugate polymer are performed in order to display the effects of t-butyl and methoxy group substitution and of kink(ortho and meta) linkage. The conjugation length of the polymers can be controlled by substituents and kink linkages of backbone. Structures for the molecules, o-, m-, and p-MBPBs as well as unsubstituted o-, m-, and p-DSBs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF method with 3-21G(d) basis set. The potential energy curves with respect to the change of single torsion angle are obtained by using semiempirical methods and ab initio HF/3-21G(d) basis set. The curves are similar shape in the molecules with respect to the position of vinylene groups. It is shown that the conformations of the molecules are compromised between the steric repulsion interaction and the degree of the conjugation. Electronic properties of the molecules were obtained by applying the optimized structures and geometries to the ZINDO/S method. ZINDO/S analysis performed on the geometries obtained by AM1 method and HF/3-21G(d) level is reported. The absorption wavelength on the geometries obtained by AM1 method is much longer than that by HF/3-21G(d) level. The absorption wavelength of MBPBs are red shifted with comparison to that of corresponding DSBs in the same torsion angle because of electron donating substituents. The absorption wavelength of isomers with kink(orth and meta) linkage is shorter than that of para linkage.