• Title/Summary/Keyword: Picosecond dynamics

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Solvent Effect on the Dynamics of Radical Ion Pair Separation

  • Han, Chul-Hee
    • Journal of Photoscience
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    • v.8 no.1
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    • pp.33-37
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    • 2001
  • Picosecond absorption spectroscopy has been employed in the study of the solvent dynamics of 1, 2, 4, 5-tetracyanobenzene/biphenyl derivative radical ion pairs, and the resulting rates of radical ion pair separation are faster in acetonitrile than in dichloromethane. In an effort to account quantitatively for such solvent effect on the rate of radical ion pair separation, an equation for the rate of radical ion pair separation is introduced, in which the rate depends exponentially on the electrostatic interaction energy in the radical ion pair. In our analysis of the types of electrostatic interaction energy based on the conducting spheres in dielectric continuum was chosen, and the rate equation employing this electrostatic energy provided information on the distance on the distance of radical ion pair separation and solvation energy of the radical ion pair, thereby providing quantitative explanation for the observed solvent effect on the rate of radical ion pair sepaaration.

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STUDY OF CONTACT ION PAIR DYNAMICS IN VIEW OF THE MOLECULAR SHAPES

  • Han, Chul-Hee
    • Journal of Photoscience
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    • v.3 no.3
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    • pp.147-151
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    • 1996
  • Dynamics of contact ion-pair between 1, 2, 4, 5-tetracyanobenzene anion and cation of biphenyl derivatives was investigated on the picosecond time scale. Solvent effect on the electron transfer was observed and electron transfer rates were examined using Marcus equation which contains distance dependence of the electron transfer rate in the frequency factor, along with the consideration of molecular shape. From the discussion based on disk model for molecular shape, contribution of interring torsional motion of biphenyl to the inner-sphere reorganization energy is strongly suggested, which leads to the physical explanation for the observed solvent effect on the rate of electron transfer.

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Study of rganized Assemblies and Surfaces Using Picosecond Lasers

  • Bhattacharyya, Kankan
    • Journal of Photoscience
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    • v.6 no.3
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    • pp.123-128
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    • 1999
  • Dynamics of many ultrafast processes are markedly slowed down in various organized molecular assemblies compared to ordinary liquids. We will show that the solvation dynamics of water molecules is affected amost dramatically and is retarded by 3 ∼4 orders of magnitude in microemulsions, micells and lipids. We will also discuss how the access to fewer water molucules and the drastically altered local pH in an organized asembly affected the excited state proton transfer processes. Finally, we will show how surface second haromonic generation can be used to study the air-water surface.

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Picosecond Dynamics of CN--Ligated Ferric Cytochrome c after Photoexcitation Using Time-resolved Vibrational Spectroscopy

  • Kim, Joo-Young;Park, Jae-Heung;Chowdhury, Salina A.;Lim, Man-Ho
    • 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.

Intramolecular Hydrogen Bonds in Proteinase Inhibitor Protein, A Molecular Dynamics Simulation Study

  • Chung, Hye-Shin
    • BMB Reports
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    • v.29 no.4
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    • pp.380-385
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    • 1996
  • Ovomucoid third domain is a serine proteinase inhibitor protein which consists of 56 amino acid residues. A fifty picosecond molecular dynamics (MD) simulation was carried out for ovomucoid third domain protein with 5 $\AA$ layer of water molecules. A comparison of main chain atoms in the MD averaged structure with the crystal structure showed that most of the backbone structures are maintained during the simulation. Investigation of the intramolecular hydrogen bondings indicated that most of the interactions between main chain atoms were conserved, whereas those between side chains were reorganized for the period of the simulation. Especially, the side chain interactions around the scissile bond of reactive site P1 (Met18) were found to be more extensive for the MD structures. During the simulation, hydrogen bonds were maintained between the side chains of Glu19 and Arg21 as well as those of Thr17 and Glu19. Extensive side chain interactions observed in the MD structures may shed light on the question of why protein proteinase inhibitors are strong inhibitors for proteinases rather than good substrates.

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Lifetime and Anisotropy Measurements of DODCI in the excited state by TCSPC (TCSPC에 의한 DODCI의 형광 소멸시간 및 비등방성 측정 연구)

  • 이민영;김동호
    • Korean Journal of Optics and Photonics
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    • v.1 no.1
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    • pp.52-57
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    • 1990
  • Employing a picosecond laser and fast electronics. we developed a time -correlated single photon counting (TCSPC) system by which ltuninescence lifetimes can be measured in the subnanosecond to microsecond scale. We also studied non-radiative decay dynamics and rotational motion of DODC! laser dye in solution using this system. ystem.

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Rapid Quenching Dynamics of F Center Excitation by $OH^-$ Defects in KCI

  • 장두전;김필석
    • Bulletin of the Korean Chemical Society
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    • v.16 no.12
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    • pp.1184-1189
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    • 1995
  • The rapid quenching dynamics of F center excitation by OH- defects in KCl crystals are investigated by monitoring ground state absorption bleach recovery, using a picosecond streak camera absorption spectrometer. F center absorption bleach in OH--doped crystals shows three distinguishable recovery components with the current temporal resolution, designated as slow, medium and fast components. The slow one is due to the normal relaxation process of F* centers as found in OH--free crystals. The others are consequent on energy transfer from electronically excited F centers to OH--vibrational levels. The fast component is a minor energy transfer process and resulting from the relaxation of somewhat distant, not the closest, associated pairs of F* and OH- defects. The energy transfer between widely separated F* and OH- defects opens up a recovery process via the medium component which is assisted by OH- librations, lattice vibrations and OH- dipole reorientations. The quenching behaviors of F* luminescence and photoionization by OH- are explained well by the relaxation process of the medium component.

F-Center Excitation Energy Transfer to CN$^-$ vibrational Levels in CsCl

  • Jang, Du-Jeon
    • Proceedings of the Optical Society of Korea Conference
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    • 1990.07a
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    • pp.94-100
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    • 1990
  • The rapid quenching dynamics of the F-center excitation by CN- defects in CsCl crystals were investigated by monitoring the ground state bleach recovery kinetics of F-centers, using a picosecond streak camera absorption spectrometer. The F-centers in CN- doped quenched samples show two bleach recovery components. Optical aggregation converts the slow component to the fast component. The slow one is due to the normal relaxation of the F*-centers as found in CN_ free crystals. The fast one is due to the energy transfer of the F-center electronic excitation to the vibrational energy levels of CN_ molecualr defects. The energy transfer occurs only in the F-center-CN_ defect pairs, FH(CN_)-centers.

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A New Method of Optical Short Pulse Generation Using Diode Lasers (다이오드 레이저를 이용한 새로운 짧은 광펄스 생성방법)

  • Lee, Chang-Hee;Cho, Kun-Ho;Shin, Sang-Yung;Lee, Soo-Young
    • Proceedings of the KIEE Conference
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    • 1987.07a
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    • pp.54-57
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    • 1987
  • A new method optical short pulse generation using diode lasers under the negative electro-optic feedback are proposed. The self-pulsing is induced by feedback itself and the pulse is formed by the interaction of feeback signal and the dynamics of the diode laser. The simulated pulse width is on the order of picosecond with several GIIz repetition rates.

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