Vibronic Enhancement of Algae Light Harvesting

Dean, Jacob C.; Mirkovic, Tihana; Toa, Zi S. D.; Oblinsky, Daniel G.; Scholes, Gregory D.

doi:10.1016/j.chempr.2016.11.002

Cited by 128 publications

(204 citation statements)

References 44 publications

(51 reference statements)

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“…For both the centred and blue-shifted laser spectra simulations, the calculated amplitude For complex systems with broad absorption bands, spectral filtering can be exploited to focus 2D spectroscopic studies on specific regions. 36,44,70,71 But as shown in this work, spectral filtering can also be employed to control the pathways involved in a non-linear measurement and predictably eliminate certain pathways. Introducing the use of multicoloured laser pulses also provides the potential for isolation of specific Liouville pathways.…”

Section: Discussionmentioning

confidence: 99%

Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model

et al. 2018

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Two-dimensional optical spectroscopy is a powerful technique for the probing of coherent quantum superpositions. Recently, the finite width of the laser spectrum has been employed to selectively tune experiments for the study of particular coherences. This involves the exclusion of certain transition frequencies, which results in the elimination of specific Liouville pathways. The rigorous analysis of such experiments requires the use of ever more sophisticated theoretical models for the optical spectroscopy of electronic and vibronic systems. Here we develop a nonimpulsive and non-Markovian model, which combines an explicit definition of the laser spectrum, via the equation of motion-phase matching approach (EOM-PMA), with the hierarchical equations of motion (HEOM). This theoretical framework is capable of simulating the 2D spectroscopy of vibronic systems with low frequency modes, coupled to environments of intermediate and slower time scales. In order to demonstrate the spectral filtering of vibronic coherences, we examine the elimination of lower energy peaks from the 2D spectra of a zinc porphyrin monomer upon blue-shifting the laser spectrum. The filtering of Liouville pathways is revealed through the disappearance of peaks from the amplitude spectra for a coupled vibrational mode.

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Section: Discussionmentioning

confidence: 99%

Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model

et al. 2018

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“…The commonly employed technique of twodimensional electronic spectroscopy (2DES) often lacks the spectral resolution to untangle the complex, congested spectra of relevant systems-making it challenging to discern whether or not an oscillatory feature is electronic, vibrational, or vibronic in nature 21 . Although recent work has successfully unveiled the presence of vibronic coupling in natural and artificial lightharvesting systems [28][29][30][31][32][33][34] , the newly developed technique of twodimensional electronic-vibrational (2DEV) spectroscopy 7,[35][36][37][38][39][40][41][42][43][44] , by focusing on vibrational transitions in the final light-matter interaction, has the potential to provide significantly improved experimental input into the interplay of electronic and nuclear dynamics in ultrafast energy (and charge) transfer. Several aspects of 2DEV spectroscopy are significant in this regard.…”

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confidence: 99%

Vibronic mixing enables ultrafast energy flow in light-harvesting complex II

et al. 2020

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Since the discovery of quantum beats in the two-dimensional electronic spectra of photosynthetic pigment-protein complexes over a decade ago, the origin and mechanistic function of these beats in photosynthetic light-harvesting has been extensively debated. The current consensus is that these long-lived oscillatory features likely result from electronic-vibrational mixing, however, it remains uncertain if such mixing significantly influences energy transport. Here, we examine the interplay between the electronic and nuclear degrees of freedom (DoF) during the excitation energy transfer (EET) dynamics of light-harvesting complex II (LHCII) with two-dimensional electronic-vibrational spectroscopy. Particularly, we show the involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states and assign observed oscillatory features to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space. These frequencies correspond to known vibrational modes of chlorophyll, suggesting that electronic-vibrational mixing facilitates rapid EET over moderately size energy gaps.

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“…One of possible origins is the vibronic coherence from the interactions between the exciton and underdamped vibrations as the vibrational frequencies are resonant with the excitonic energy gap, first proposed by Christensson et al From then on, more and more attentions have been paid on the role of these vibrations on the beating signals as well as the corresponding carrier dynamics. It is now accepted that the underdamped vibrations with resonant frequencies may facilitate the EET, charge separation and singlet fission, which have largely extended the knowledge about resonant vibration‐assisted carrier dynamics. Along this way, various fascinating results have been obtained.…”

Section: Introductionmentioning

confidence: 99%

“…Along this way, various fascinating results have been obtained. The well‐designed experiments on the photosystem II reaction center, light‐harvesting complex II, cryptophyte light‐harvesting protein PC645 and conjugated polymers have shown the vibronic natures of the observed long‐lasting coherent dynamics and have demonstrated their tight connections to the ultrafast EET and charge separation processes. Theoretically, various calculations have confirmed the existence of resonant vibration‐assisted ultrafast carrier dynamics, and the resonant frequency has been demonstrated to be relevant to the reorganization energy .…”

Section: Introductionmentioning

confidence: 99%

Effect of an underdamped vibration with both diagonal and off‐diagonal exciton–phonon interactions on excitation energy transfer

Wang

Zhao

2018

J Comput Chem

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A numerically exact approach, named as the hierarchical stochastic Schrödinger equation, is employed to investigate the resonant vibration-assisted excitation energy transfer in a dimer system, where an underdamped vibration with both diagonal and off-diagonal exciton-phonon interactions is incorporated. From a large parameter space over the site-energy difference, excitonic coupling, and reorganization energy, it is found that the promotion effect of the underdamped vibration is significant only when the excitonic coupling is smaller than the site-energy difference. Under the circumstance, there is an optimal strength ratio between diagonal and off-diagonal excitonphonon interactions for the resonant vibration-assisted excitation energy transfer as the site-energy difference is greater than the reorganization energy, whereas in the opposite situation the most efficient energy transfer occurs as the exciton-phonon interaction is totally off-diagonal.

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Vibronic Enhancement of Algae Light Harvesting

Cited by 128 publications

References 44 publications

Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model

Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model

Vibronic mixing enables ultrafast energy flow in light-harvesting complex II

Effect of an underdamped vibration with both diagonal and off‐diagonal exciton–phonon interactions on excitation energy transfer

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