• 제목/요약/키워드: Picosecond dynamics

검색결과 13건 처리시간 0.022초

Solvent Effect on the Dynamics of Radical Ion Pair Separation

  • Han, Chul-Hee
    • Journal of Photoscience
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    • 제8권1호
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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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    • 제3권3호
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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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    • 제6권3호
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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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    • 제31권12호
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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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    • 제29권4호
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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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TCSPC에 의한 DODCI의 형광 소멸시간 및 비등방성 측정 연구 (Lifetime and Anisotropy Measurements of DODCI in the excited state by TCSPC)

  • 이민영;김동호
    • 한국광학회지
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    • 제1권1호
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    • pp.52-57
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    • 1990
  • 피코초 레이저와 고속 전자장치를 사용하여 subnanosecond에서 microsecond 넓은 범위에 걸쳐서 발광 소멸 시간을 측정할 수 있는 time-correlated single photon counting(TCSPC) 장치를 개발하였다. 이 TCPSC를 사용하여 색소레이저에 있어서 saturable absorber로 많이 쓰이는 DODCI의 소멸시간 및 회전 완화시간을 측정함으로써 여기상태에서의 동력학과 회전운동에 관해 연구하였다.

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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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    • 제16권12호
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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
    • 한국광학회:학술대회논문집
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    • 한국광학회 1990년도 광학 및 양자전자학 워크샵
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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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다이오드 레이저를 이용한 새로운 짧은 광펄스 생성방법 (A New Method of Optical Short Pulse Generation Using Diode Lasers)

  • 이창희;조건호;신상영;이수영
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 1987년도 전기.전자공학 학술대회 논문집(I)
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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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