• Bulletin of the Korean Chemical Society
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• v.12 no.4
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• pp.441-444
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• 1991

The intramolecular proton transfers of 2-hydroxy-4,5-naphthotropone in room temperature solutions are studied using static and time-resolved absorption and emission spectroscopy. Dual normal and tautomer fluorescence is observed in ethanol solution, while only the tautomer fluorescence is observed in cyclohexane solution. The fluorescence lifetimes and quantum yields in ethanol and cyclohexane solutions indicate that in hydrocarbon solvents, rapid intersystem crossing competes with proton transfer in the first excited singlet state. Transient absorption spectra and kinetics indicate that proton transfer also undergoes in the first triplet state with a transfer time of ∼ 3 ns. No transient absorption from the tautomer ground state indicates a rapid back proton transfer in the ground state.

• Korean Journal of Optics and Photonics
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• v.2 no.4
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• pp.209-213
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• 1991

Recently, the developments in generating and amplifying ultrashort optical pulses $(ps=10^{-12}s or fs=10^{-15}s)$ have imposed on great advances in the time-resolved laser spectroscopy. Especially, the transient absorption spectroscopy has a wide application range and the main idea of this technique is pump & probe method. After the pump pulse makes the material an excited or a transient states, the probe pulse is sent through the material to measure the absorbance change due to the transient states. Here, if the absorbance change was measured by the time delay between pump & probe pulses, the dynamic information of the excited or the transient states (the transient abnsorption changes by time & wavelength) can be obtained. At our laboratory, the ultrashort optic1 pulse (

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3771-3776
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• 2010

The dynamics of the $CN^-$-ligated ferric cytochrome c (CytcCN) in $D_2O$ at 283 K following Q-band photoexcitation at 575 nm was observed using femtosecond time-resolved vibrational spectroscopy. The equilibrium vibrational spectrum of the CN stretching mode of CytcCN shows two overlapping bands: one main band (82%) at $2122\;cm^{-1}$ with $23\;cm^{-1}$ full width at half maximum (fwhm) and the other band (18%) at $2116\;cm^{-1}$ with $7\;cm^{-1}$ fwhm. The time-resolved spectra show bleaching of the CN fundamental mode of CytcCN and two absorption features at lower energies. The bleach signal and both absorption features are all formed within the time resolution of the experiment (< 200 fs) and decay with a life time of 1.9 ps. One transient absorption feature, appearing immediately red to the bleach signal, results from the thermal excitation of low-frequency modes of the heme that anharmonically couple to the CN fundamental mode, thereby shifting the CN mode to lower energies. The shift of the CN mode decays with a lifetime of 2 ps, equivalent to the time scale for vibrational cooling of the low-frequency heme modes. The other transient absorption feature, which is 3.3 times weaker than the bleach signal and shifted $27\;cm^{-1}$ toward lower energies, is attributed to the CN mode in an electronically excited state where the CN bond is weakened with a lowered extinction coefficient. These observations suggest that photoexcited CytcCN mainly undergoes ultrafast radiationless relaxation, causing photo-deligation of $CN^-$ from CytcCN highly inefficient. As also observed in $CN^-$-ligated myoglobin, inefficient ligand photodissociation might be a general property of $CN^-$-ligated ferric hemes.

• Journal of the Optical Society of Korea
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• v.1 no.1
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• pp.15-18
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• 1997

Intensity dependent dynamics of photoinduced absorption in $CdS_{0.4}$/$Se_{0.6}$ semiconductor doped glasses below the band gap was investigated by using time-resolved differential transmittance spectroscopy. The carriers populated through ultrafast trapping at semiconductor-glass interfaces give rise to a broad photoinduced absorption below the band gap. The decay time of transient absorption depends strongly on the excitation intensity. Based on our results, the physical mechanism for photoinduced absorption processes was suggested.

• Bulletin of the Korean Chemical Society
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• v.24 no.11
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• pp.1675-1679
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• 2003

The photodynamics of excited-state intramolecular proton transfer reaction of 1-hydroxyanthraquinone (1-HAQ) and 1-deuterioanthraquinone was investigated in toluene with time-resolved emission and femtosecond transient transmittance techniques at room temperature. The temporal profiles of transient transmittance of 1-HAQ could be well described with multi-decaying time constants. The ultrafast time constant within ca. 260 fs reflects the dynamics of proton transfer. The decay component of 2 ps is assigned to an additional proton translocation process induced by the intramolecular vibrational relaxation, whereas the decay component of 18 ps is assigned to the vibrational cooling process, while the long component (200 ps) can be explained in terms of the relaxation from excited-state keto-tautomer to its ground state. Time-resolved anisotropy decay dynamics and isotope effects on the photodynamics reveals that the ESIPT from enol-tautomer to keto-one of 1-HAQ is barrierless reaction and coupled to a vibrational relaxation process.

• Journal of Photoscience
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• v.10 no.1
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• pp.97-104
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• 2003

The excitation wavelength dependence of laser ablation dynamics of an azobenzene-containing urethane-urea copolymer film was investigated by measuring the laser fluence dependence of etch depth, transient absorbance change at each excitation wavelength, and transient absorption spectra. Moreover expansion/contraction dynamics was studied by applying nanosecond time-resolved interferometry. The threshold was determined at several excitation wavelengths from etch depth measurement, while time-integrated absorbance was obtained under excitation conditions. The photon energy required to remove the topmost of surface layer of the film did not .depend on excitation wavelength, and the penetration depth of excitation pulse dominated the etch depth. When the excitation wavelength was longer than 500 nm, permanent swelling was clearly observed but not for shorter wavelength excitation. In the latter case, photoisomerization occurred during excitation and the following photoreduction may play an important role. On the basis of the observations made in this study, a photochemical and photothermal mechanisms can explain mostly the short and long wavelength excitation results, respectively.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1967-1972
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• 2007

Photophysical properties of a newly-synthesized porphyrin derivative, trans-bis(ferrocene carboxylato)- (5,10,15,20-tetraphenylporphyrinato)tin(IV) [Sn(TPP)(FcCOO)2] were investigated by means of steady-state and fs-time resolved laser spectroscopic techniques, and compared with those of a standard molecule, trans-dichloro( 5,10,15,20-tetraphenyl-porphrinato)tin(IV) [Sn(TPP)Cl2]. The fluorescence spectrum of Sn(TPP)- (FcCOO)2 was observed to exhibit dual emission bands originating from the S2-state and the S1-state, which was greatly quenched as compared to those of Sn(TPP)Cl2. The fs-time resolved fluorescence and transient absorption spectroscopic measurements revealed that the fluorescence quenching is due to formation of the long-lived charge transfer state by intramolecular electron transfer from ferrocene to the S2-excited SnTPP in addition to the enhanced non-radiative deactivation processes.

• Journal of Photoscience
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• v.4 no.3
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• pp.113-119
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• 1997

The synthesis and excited-state dynamics are described for a tetrad (ZC - ZP - ZP - I) consisting of zinc chlorin (ZC), zinc porphyrin (ZP), zinc porphyrin (ZP), and pyromellitimide (I), which upon photoexcitation provides a fully charge-separated state (ZC$^+$- P - ZP - l$^- $) with lifetimes of 230 $\mu$s in THF and > 50$ \mu$s in DMF at room temperature via a stepwise electron-transfer relay that has been detected by the ps-time resolved transient absorption spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.22 no.2
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• pp.219-227
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• 2001

The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (Ia /Ib) of DMABA in the aqueous $\alpha-CD$ solutions are greatly decreased while the Ia /Ib values in the aqueous B-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in $\alpha-CD$ or B-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of νs (CO2-)(1380 cm-1 ) with appearance of ν(C-OH)(1280 cm -1) band, respectively. Thus, in the aqueous B-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen-bonded with the secondary hydroxyl group of B-CD while in aqueous and $\alpha-CD$ solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous B-CD solutions the enhancement of the Ia /Ia value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of B-CD as well as the lower polarity of the rim of the B-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/ B-CD complex in the presence of silver colloids.