• Title/Summary/Keyword: Excited state

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Determination of Reactivity by MO Theory (VIII). PMO Interpretation for Photocyclodehydrogenation of o-Terphenyl-type compounds (화학반응성의 분자궤도론적 연구 (제8보). o-Terphenyl 형 화합물의 광학적탈수소 고리화 반응에 대한 섭동분자궤도론적 해석)

  • Ikchoon Lee;Bonsu Lee
    • Journal of the Korean Chemical Society
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    • v.20 no.2
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    • pp.136-140
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    • 1976
  • The photocyclodehydrogenation reaction of o-terphenyl type compounds has been interpreted with perturbational molecular orbital theory. Results show that the mobile bond order for the first excited state is a good reactivity index and this approach is also consistent with the orbital symmetry conservation rule of Woodward and Hoffmann.

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Photoreactivity and Thermogravimetry of Copper(II) Complexes of N-Salicylideneaniline and Its Derivatives

  • Osman, Ahmed H.;Aly, Aref A.M.;El-Mottaleb, Mohamed Abd;Gouda, Gamal A.H.
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.45-50
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    • 2004
  • $Cu^{II}$-complexes of N-salicylideneaniline and its derivatives were not light sensitive in most solvents such as acetonitrile. A photo-decomposition occurred upon irradiation in halocarbon solvents such as $CHCl_3$. It has been suggested that such photoreactivity is attributed to the reactivity of charge-transfer to solvent (CTTS) excited state attained upon irradiation. A mechanism has been proposed to account for the results obtained. The complexes have been thermally analysed in nitrogen and static air using thermogravimetry (TG) and derivative thermogravimetry (DTG). The thermal degradation of the complexes proceeds in two or three stages. The kinetic parameters obtained from the Coats-Redfern and Horowitz-Metzger equations show the kinetic compensation effect.

Analysis of D-C Shunt Motor Characteristics, driving D-C Series Generator (직통직권 발전기에 의한 직통분권 전동기의 특성해석)

  • 이승원;한송엽
    • 전기의세계
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    • v.16 no.1
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    • pp.7-13
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    • 1967
  • There are many kinds of motors operating by rated voltage which is constant. In this paper, the characteristics of separately excited direct current motor is analyzed when its terminal voltage is varied as its load current. As for this source, direct current generator of a series field is used, and it is driven at constant speed by a primemover. The induced voltage of the generator is propotional to its load current but it saturates as its load current is large. The charateristics of motor is studied by analog computer because of the nonlinearity of generator. The results are as follows: (1) The load current and the rotor speed of motor increase as the load of motor increases. But the speed of rotor decreases for the influence of the saturation of the iron of generator field when its load current is large. (2) Decreasing the inertia of motor and increasing the inductance of the armature circuit improve the stability of motor and the region of stable state. (3) By changing the field current of the motor, the speed and the direction of rotor can be controlled in wide range.

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Photochemical and Thermal Solvolysis of Picolyl Chlorides

  • Shim Sang Chul;Choi Seung Ju
    • Bulletin of the Korean Chemical Society
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    • v.3 no.1
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    • pp.30-33
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    • 1982
  • Photochemical and thermal solvolysis of 2,3,4-picolyl chlorides (2,3,4-PC) were studied in amine solvents and the results were correlated with the electronic structures calculated by PPP-SCF-MO CI method. Activation parameters show that the thermal solvolysis of PC is $S_N2$ type rcaction. The rates of thermal reaction in pyridine or t-butylamine solvent decrease in the order of 2-PC > 3-PC > 4-PC. These results are consistent with the predictions based on the electron densities of picolyl chlorides. In photosolvolysis, the same products as those of thermal reactions were obtained. The results indicate that photochemical solvolysis undergoes through heterolytic cleavage. Relative quantum yields of photosolvolysis of 2,3,4-picolyl chlorides in t-butylamine solvent were determined to be 0.73, 1, and 0.50 respectively. These results are in good agreement with the electron densities of the excited triplet state of picolyl chlorides.

The out-of-plane Band Contour of Dichloroborane Molecules

  • Lee, Kuk-Haeng;Kim, Ja-Hong;Sohn, Sung-Ho;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.147-149
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    • 1987
  • The out-of-plane bending, vibrational-rotational FT-IR spectra of dichloroborane molecule were analyzed. The band centers are 785.992, 785.723, 647.217, and 646.997 $cm^{-1}$ and centrifugal distortion constants are $2.2{\times}10^{-6},\;5.5{\times}10^{-6},\;0.2{\times}10^{-6}$, and $0.7{\times}10^{-6}cm^{-1}$ for $H^{11}B^{35}Cl_2$, $H^{11}B^{35}Cl^{37}Cl$, $D^{11}B^{35}Cl_2$, and $D^{11}B^{35}Cl^{37}Cl$, respectively. The theoretical spectrum of $D^{11}B^{36}Cl_2$ was plotted to conform the molecular constants and the rotational constants for the first excited vibrational state of this molecule were A' = 1.165932, B' = 0.106166, and C' = 0.097229 $cm^{-1}$. The calculated spectra were in good agreement with the observed spectra.

The New Substituent Constants in the Excited States (II)

  • Sang-Chul Shim;Joon-Won Park;Heui-Suk Ham;Jin-Soon Chung
    • Bulletin of the Korean Chemical Society
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    • v.4 no.1
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    • pp.45-47
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    • 1983
  • In order to standardize the ${\sigma}^*,\;{\rho}^*$ is taken as unity for the benzoic acids by analogy with the fact that ${\rho}$ of benzoic acids in the ground state is taken as unity. The $pK_{\alpha}^*$ of many benzoic acid derivatives are determined by UV spectroscopy and fluorescence spectral analysis whenever possible. The ${\sigma}^*$ constants are derived from the Hammett equation utilizing these $pK_{\alpha}^*$ values and the $pK_{\alpha}^*$ of the benozic acid derivatives showed better correlationship with ${\sigma}^*$ than ${\sigma},\;{\sigma}^+\;and\;{\sigma}^-$ as expected. From these ${\sigma}^*$ values, ${\rho}^*$ of the phenol derivatives was calculated to be 1.28. The new standardized ${\sigma}^*$ values are calculated from the $pK_{\alpha}^*$ values of phenols since more accurate and abundant data are available for phenols than the benzoic acid derivatives.

Preparation and Photophysical Properties of 4-(9-Anthrylethenyl)-4'-methyl-2,2'-bipyridine and Its Ruthenium Bipyridyl Complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$

  • 배은영;신은주
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.86-93
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    • 1998
  • Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

Fluorescence Enhancement of Ethidium Bromide by DNA Bases and Nucleosides

  • Pyun, Chong-Hong;Park, Su-Moon
    • Bulletin of the Korean Chemical Society
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    • v.10 no.2
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    • pp.142-147
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    • 1989
  • Fluorescence enhancements of ethidium bromide (EB) by solution species of low molecular weights such as DNA base molecules and nucleosides in water are reported. The degree of enhancements was determined by intensity as well as lifetime measurements for EB fluorescence. Experiments including solvent effects on absorbance and fluorescence spectra of EB, effects of protonation on the EB absorbance spectrum, and determination of equilibrium constants for EB-DNA bases have been performed to help explain the fluorescence enhancement. The results suggest that the excited state stabilization in the hydrophobic environment, the loss of torsional/vibrational energy of amino groups, and the change in the electronic transition characteristics are all responsible for the fluorescence enhancement.

Micellar Effects on Intramolecular Charge Transfer Emission from Biphenylcarboxylic Acids

  • Yoon, Min-Joong;Cho, Dae-Won;Kang, Seong-Gwan;Lee, Min-Yung
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.704-708
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    • 1993
  • The intramolecular charge transfer (ICT) phenomena of the photoexcited 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid (4BPCA) have been investigated in some surfactant micellar solutions. The ICT emission of 4BPCA and 2BPCA in aqueous solution at sufficiently low pH (1-3) has been observed to be markedly quenched and blue-shifted upon addition of a cationic surfactant, cetyltrimethylammonium chloride (CTAC) in contrast to little change in anionic sodium dodecyl sulfate (SDS) and neutral Brij 35. An anionic emission band has been observed to be enhanced at expense of the ICT emission as a function of the concentration of CTAC. These results with the micellar effects on the fluorescence decay kinetics of 4BPCA suggest that formation of the ICT state of the excited acids is inhibited by CTAC-induced proton transfer as well as the decrease in the polarity and/or hydrogen-bonding ability of the micellar microenvironment entrapping the acids.

Effect of Cations on the open-Circuit Photovoltage and the Charge-Injection Efficiency of Dye-Sensitized Nanocrys-talline Rutile $TiO_2$ Films

  • Park, Nam Gyu;Jang, Sun Ho;Kim, Gang Jin
    • Bulletin of the Korean Chemical Society
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    • v.21 no.10
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    • pp.1047-1048
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    • 2000
  • Dye-sensitized nanocrystalline rutile $TiO_2$ solar cells were prepared, and the influence of Li+ and 1,2-dimethyl-3-hexyl imidazolium ions in the electrolyte on the photovoltaic properties was compared. The electrolyte con-taining Li+ ions produced a lower open-circuit photovoltage than the electrolyte with 1,2-dimethyl-3-hexyl im-idazolium ions, suggesting that the adsorption of Li+ ions to the rutile $TiO_2$ surface causes a shift in the band edges toward more positive potentials. At the same time, both the short-circuit photocurrent and the maximum value of the incident-photon-current conversion efficiency (IPCE) of the electrolyte containing Li+ ions were relatively higher. Data analysis suggests that presence of adsorbed Li+ ions improves via the phenomenon of band-edge movement the charge-injection efficiency by altering both the energy and number of excited state levels of the dye that participate in electron injection.