Two-Level-System Relaxation in Amorphous Solids as Probed by Nonphotochemical Hole-Burning in Electronic Transitions

Hayes, John M.; Jankowiak, Ryszard; Small, Gerald J.

doi:10.1007/978-3-642-83290-1_5

Cited by 20 publications

(17 citation statements)

References 109 publications

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“…This dependence is the signature for spectral dynamics stemming from coupling to the glass-like two-level system (TLS) of the protein (see, e.g. Völker (46) and Hayes et al (48)), cf Discussion section. The inset of Fig.…”

Section: Methodsmentioning

confidence: 99%

Assignment of the Lowest QY-state and Spectral Dynamics of the CP29 Chlorophyll a/b Antenna Complex of Green Plants: A Hole-burning Study ‡

Pieper

Irrgang

Rätsep

et al. 2007

Photochemistry and Photobiology

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Low‐temperature absorption, fluorescence and persistent nonphotochemical hole‐burned spectra are reported for the CP29 chlorophyll (Chl) a/b antenna complex of photosystem II of green plants. The absorption‐origin band of the lowest Qy‐state lies at 678.2 nm and carries a width of ∼130 cm−1 that is dominated by inhomogeneous broadening at low temperatures. Its absorption intensity is equivalent to that of one of the six Chl a molecules of CP29. The absence of a significant satellite hole structure produced by hole burning, within the absorption band of the lowest state, indicates that the associated Chl a molecule is weakly coupled to the other Chl and, therefore, that the lowest‐energy state is highly localized on a single Chl a molecule. The electron–phonon coupling of the 678.2 nm state is weak with a Huang–Rhys factor S of 0.5 and a peak phonon frequency (ωm) of ∼20 cm−1. These values give a Stokes shift (2Sωm) in good agreement with the measured positions of the absorption band at 678.2 nm and a fluorescence‐origin band at 679.1 nm. Zero‐phonon holes associated with the lowest state have a width of ∼0.05 cm−1 at 4.2 K, corresponding to a total effective dephasing time of ∼400 ps. The temperature dependence of the zero‐phonon holewidth indicates that this time constant is dominated at temperatures below 8 K by pure dephasing/spectral diffusion due to coupling of the optical transition to the glass‐like two‐level systems of the protein. Zero‐phonon holewidths obtained for the Chl b bands at 638.5 and 650.0 nm, at 4.2 K, lead to lower limits of 900 ± 150 fs and 4.2 ± 0.3 ps, respectively, for the Chl b→ Chl a energy‐transfer times. Downward energy transfer from the Chl a state(s) at 665.0 nm occurs in 5.3 ± 0.6 ps at 4.2 K.

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Section: Methodsmentioning

confidence: 99%

Assignment of the Lowest QY-state and Spectral Dynamics of the CP29 Chlorophyll a/b Antenna Complex of Green Plants: A Hole-burning Study ‡

Pieper

Irrgang

Rätsep

et al. 2007

Photochemistry and Photobiology

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“…46 Thus, the former are most likely attributed to delocalized vibrations of the amorphous protein matrix (see e.g. Hayes et al 47 ). On the other hand, it is possible that localized vibrations contribute to the high-frequency tail of the onephonon profile (>50 cm -1 ).…”

Section: Simulations Of Fluorescence Spectra At 42 K Recent Holeburmentioning

confidence: 98%

Electron−Phonon Coupling in Solubilized LHC II Complexes of Green Plants Investigated by Line-Narrowing and Temperature-Dependent Fluorescence Spectroscopy

et al. 2001

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Line-narrowed and temperature-dependent fluorescence spectra are reported for the solubilized trimeric lightharvesting complex of Photosystem II (LHC II). Special attention has been paid to eliminate effects owing to reabsorption and to ensure that the line-narrowed fluorescence spectra are virtually unaffected by hole burning or scattering artifacts. Analysis of line-narrowed fluorescence spectra at 4.2 K indicates that the lowest Q y -state of LHC II is characterized by weak electron-phonon coupling with a Huang-Rhys factor of ∼ 0.9 and a broad and strongly asymmetric one-phonon profile with a peak frequency ω m of 15 cm -1 and a width of Γ ) 105 cm -1 . The 4.2 K fluorescence data are further consistent with the assignment of the lowest Q y -state at ∼ 680.0 nm and an inhomogeneous width of ∼80 cm -1 gathered from a recent hole-burning study (Pieper et al. J. Phys. Chem. A 1999, 103, 2412. The temperature dependence of the fluorescence spectra of LHC II is simulated using the low-energy Q y -level structure reported in the latter study as well as the parameters of electron-phonon coupling determined in the present study. Up to a temperature of 120 K, the calculations reveal that this model satisfactorily describes the basic features of the fluorescence spectra such as thermal broadening and, especially, the blue-shift of the fluorescence peak with increasing temperature. An unexpected red-shift of the fluorescence peak above 150 K is attributed to conformational changes of the protein environment. The shape of the temperature-dependent fluorescence spectra indicates that the low-energy Q ystates are populated according to a Boltzmann distribution representing the thermal equilibrium of excitation energy.

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“…Analysis of the AB = 824 -820 nm spectra in Figure 5 revealed that the 18 cm-' pseudo-PSBH and holes a 4 attain their maximum intensity (A-absorbance value) when they are located near the maximum of the 825 nm band. From hole burning theory [22], this is consistent with the satellite hole structure being due to pseudo-PSBH, vide in$% (In what follows our use of the term phonon is meant to encompass low frequency intermolecular modes and very low frequency intramolecular modes of BChl a. [23]) The intensities of holes a -d relative to the 18 cm-' pseudo-PSBH, as estimated on the basis of spectra where holes a -d and the 18 crn-' pseudo-PSBH are near the maximum of the 825 rn absorption band, are given in Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…that are described by a static distribution of TLS [6,22,23]. As depicted in Figure 2.3, excitation at the frequency wB is followed by a tunneling process in the excited state, which is typically -1000 times more favored than in the ground state, and finally relaxation to the ground state on the right.…”

Section: Hole-burning Mechanismsmentioning

confidence: 99%

Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

Matsuzaki

2001

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Two-Level-System Relaxation in Amorphous Solids as Probed by Nonphotochemical Hole-Burning in Electronic Transitions

Cited by 20 publications

References 109 publications

Assignment of the Lowest QY-state and Spectral Dynamics of the CP29 Chlorophyll a/b Antenna Complex of Green Plants: A Hole-burning Study ‡

Assignment of the Lowest QY-state and Spectral Dynamics of the CP29 Chlorophyll a/b Antenna Complex of Green Plants: A Hole-burning Study ‡

Electron−Phonon Coupling in Solubilized LHC II Complexes of Green Plants Investigated by Line-Narrowing and Temperature-Dependent Fluorescence Spectroscopy

Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

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