Coupling of multi-vibrational modes in bacteriochlorophyll a in solution observed with 2D electronic spectroscopy

Yue, Shuai; Wang, Zhuan; Leng, Xuan; Zhu, Ruidan; Chen, Hailong; Weng, Yuxiang

doi:10.1016/j.cplett.2017.03.029

Cited by 19 publications

(17 citation statements)

References 48 publications

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“…The BChl spectrum shows many prominent modes (Fig. 2a) which have been previously attributed to purely vibrational coherences and are well described by a displaced oscillator model 33,[40][41][42] . There is very high agreement of the peak locations in the monomer and BRC Frobenius spectra.…”

Section: Two-dimensional Electronic Spectroscopy Of the Brcsupporting

confidence: 56%

Hidden vibronic and excitonic structure and vibronic coherence transfer in the bacterial reaction center

et al. 2022

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We report two-dimensional electronic spectroscopy (2DES) experiments on the bacterial reaction center (BRC) from purple bacteria, revealing hidden vibronic and excitonic structure. Through analysis of the coherent dynamics of the BRC, we identify multiple quasi-resonances between pigment vibrations and excitonic energy gaps, and vibronic coherence transfer processes that are typically neglected in standard models of photosynthetic energy transfer and charge separation. We support our assignment with control experiments on bacteriochlorophyll and simulations of the coherent dynamics using a reduced excitonic model of the BRC. We find that specific vibronic coherence processes can readily reveal weak exciton transitions. While the functional relevance of such processes is unclear, they provide a spectroscopic tool that uses vibrations as a window for observing excited state structure and dynamics elsewhere in the BRC via vibronic coupling. Vibronic coherence transfer reveals the upper exciton of the "special pair" that was weakly visible in previous 2DES experiments.

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Section: Two-dimensional Electronic Spectroscopy Of the Brcsupporting

confidence: 56%

Hidden vibronic and excitonic structure and vibronic coherence transfer in the bacterial reaction center

et al. 2022

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“…µ gi (µ ei ) is the reduced mass of the ground (excited) state, ω gi (ω ei ) is the frequency of the oscillator on the ground (excited) state, d i is the displacement of the origin on the excited-state potential relative to the ground state along the coordinate q i , and ω eg is the energy difference between the minima of the two electronic states. An assumption is made that the nuclear potential surfaces are well described as harmonic and that the excited energy surface is allowed to differ in curvature, giving rise to that the values of ω ei and ω gi can be different [62,63]. The oscillator strength for the vibronic transition is determined by the Frank-Condon factor while each vibrational mode contributes with a weight given by its Huang-Rhys factor in terms of difference of the mode displacement of the initial and final nuclear configurations, i.e., the extent for the wavefuction overlap of nuclear part between the initial and the final states [64−66].…”

Section: Single-vibrational Mode Versus Multi-vibrational Mode Coumentioning

confidence: 99%

Detection of Electronic Coherence via Two-Dimensional Electronic Spectroscopy in Condensed Phase

Weng

2018

Chinese Journal of Chemical Physics

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Two dimensional Fourier transform electronic spectroscopy (2DES) in the visible region enables direct observation of complex dynamics of molecules including quantum coherence in the condensed phase. This review aims to provide a bridge between the principles and intuitive physical description of 2DES for tutorial purpose. Special emphasis is laid upon how 2DES circumvents the restrictions from both uncertainty principle and the wave-packet collapse during the coherent detection, leading to the successful detection of the coherence in terms of energy difference between the eigenstates showing as the quantum beats; then upon the possible mixing among the pure electronic transition, single-mode and multi-mode coupled vibronic transition leading to the observed beating phenomena. Finally, recent advances in experimentally distinguishing between the electronic coherence and the vibrational coherence are briefly discussed.

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“…Given these similarities, it might be expected that coherences would be present in BChla as they were seen in Chla. To this effect, a recent 2DES study of coherences on the red edge of the BChla Q y band showed several coherences that were assigned to vibrational origins; 44 however, only a few lowfrequency modes were observed due to the bandwidth of the pulses used.…”

mentioning

confidence: 99%

“…Coherent dynamics have been observed in a wide variety of systems using ultrafast spectroscopy techniques, including a variety of photosynthetic proteins including BRCs, − the Photosystem II D1D2 reaction center, − various antenna protein complexes, ,− and monomeric molecular systems, including photosynthetic pigments. ,− There have been numerous theoretical studies that have sought to characterize the origin of these coherences by modeling the spectroscopic signatures of electronic, vibrational, and vibronic coherence to be expected in 2DES experiments. − A number of studies have explored the effect of vibrational–electronic resonances on enhancing the processes of EET ,− and CS. ,, …”

mentioning

confidence: 99%

Characterization of Vibrational Coherence in Monomeric Bacteriochlorophyll a by Two-Dimensional Electronic Spectroscopy

Policht

Niedringhaus

Ogilvie

2018

J. Phys. Chem. Lett.

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Bacteriochlorophyll a (BChla) is the most abundant pigment found in the Bacterial Reaction Center (BRC) and light-harvesting proteins of photosynthetic purple and green bacteria. Recent two-dimensional electronic spectroscopy (2DES) studies of photosynthetic pigment–protein complexes including the BRC and the Fenna–Matthews–Olson (FMO) complex have shown oscillatory signals, or coherences, whose physical origin has been hotly debated. To better understand the observations of coherence in larger photosynthetic systems, it is important to carefully characterize the spectroscopic signatures of the monomeric pigments. Prior spectroscopic studies of BChla have differed significantly in their observations, with some studies reporting little to no coherence. Here we present evidence of strong coherences in monomeric BChla in isopropanol using 2DES at 77 K. We resolve many modes with frequencies that correspond well with known vibrational modes. We confirm their vibrational origin by comparing the 2D spectroscopic signatures with expectations based on a purely vibrational model.

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Coupling of multi-vibrational modes in bacteriochlorophyll a in solution observed with 2D electronic spectroscopy

Cited by 19 publications

References 48 publications

Hidden vibronic and excitonic structure and vibronic coherence transfer in the bacterial reaction center

Hidden vibronic and excitonic structure and vibronic coherence transfer in the bacterial reaction center

Detection of Electronic Coherence via Two-Dimensional Electronic Spectroscopy in Condensed Phase

Characterization of Vibrational Coherence in Monomeric Bacteriochlorophyll a by Two-Dimensional Electronic Spectroscopy

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