A polarization scheme that resolves cross-peaks with transient absorption and eliminates diagonal peaks in 2D spectroscopy

Farrell, Kieran M; Yang, Nan; Zanni, Martin T.

doi:10.1073/pnas.2117398119

Cited by 24 publications

(18 citation statements)

References 68 publications

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“…Previous studies have used different methods to deconvolve 2DES dynamics in spectrally congested systems including global analysis, lifetime density analysis, and cross-peak enhancing pulse sequences . Polarization control has also been leveraged in many 2DES and 2D infrared spectroscopy studies to extract chiral, coherence-specific , and cross-peak-specific ,,− dynamics. To suppress spectral congestion and selectively watch energy transfer dynamics within the phycobilisome, we used a 2DES pulse sequence that suppresses signals arising from four interactions with parallel transition dipole moments.…”

Section: Resultsmentioning

confidence: 99%

“…The suppression is achieved by independently controlling the polarization of all pulses . The diagonal-suppressing sequence is encoded into the beam polarizations as {90, 60, 120, 0°} , or {60, 120, 0, 0°}, , where the first two pulses are pump pulses, the third is the probe, and the fourth is the local oscillator pulse. Suppressed signals include diagonal signals as well as off-diagonal signals arising from Stokes shifts and ultrafast solvation, as these processes typically do not strongly reorient the transition dipole.…”

Section: Resultsmentioning

confidence: 99%

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Phycobilisome’s Exciton Transfer Efficiency Relies on an Energetic Funnel Driven by Chromophore–Linker Protein Interactions

Sohoni,

Lloyd,

Hitchcock

et al. 2023

J. Am. Chem. Soc.

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The phycobilisome is the primary light-harvesting antenna in cyanobacterial and red algal oxygenic photosynthesis. It maintains near-unity efficiency of energy transfer to reaction centers despite relying on slow exciton hopping along a relatively sparse network of highly fluorescent phycobilin chromophores. How the complex maintains this high efficiency remains unexplained. Using a two-dimensional electronic spectroscopy polarization scheme that enhances energy transfer features, we directly watch energy flow in the phycobilisome complex of Synechocystis sp. PCC 6803 from the outer phycocyanin rods to the allophycocyanin core. The observed downhill flow of energy, previously hidden within congested spectra, is faster than timescales predicted by Forster hopping along single rod chromophores. We attribute the fast, 8 ps energy transfer to interactions between rod-core linker proteins and terminal rod chromophores, which facilitate unidirectionally downhill energy flow to the core. This mechanism drives the high energy transfer efficiency in the phycobilisome and suggests that linker protein− chromophore interactions have likely evolved to shape its energetic landscape.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Phycobilisome’s Exciton Transfer Efficiency Relies on an Energetic Funnel Driven by Chromophore–Linker Protein Interactions

Sohoni,

Lloyd,

Hitchcock

et al. 2023

J. Am. Chem. Soc.

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“…If some of the pulses/polarizations are identical, eqs can be further simplified. Various anisotropy parameters − can directly be computed by using eqs and . If molecular reorientation cannot be neglected on the time scale of the 4WM experiment, the present analysis can be generalized along the lines developed in refs − .…”

Section: C1 Transient-absorption Pump-probe Signalmentioning

confidence: 99%

Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

2022

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Femtosecond nonlinear spectroscopy is the main tool for the time-resolved detection of photophysical and photochemical processes. Since most systems of chemical interest are rather complex, theoretical support is indispensable for the extraction of the intrinsic system dynamics from the detected spectroscopic responses. There exist two alternative theoretical formalisms for the calculation of spectroscopic signals, the nonlinear response-function (NRF) approach and the spectroscopic equation-of-motion (EOM) approach. In the NRF formalism, the system–field interaction is assumed to be sufficiently weak and is treated in lowest-order perturbation theory for each laser pulse interacting with the sample. The conceptual alternative to the NRF method is the extraction of the spectroscopic signals from the solutions of quantum mechanical, semiclassical, or quasiclassical EOMs which govern the time evolution of the material system interacting with the radiation field of the laser pulses. The NRF formalism and its applications to a broad range of material systems and spectroscopic signals have been comprehensively reviewed in the literature. This article provides a detailed review of the suite of EOM methods, including applications to 4-wave-mixing and N-wave-mixing signals detected with weak or strong fields. Under certain circumstances, the spectroscopic EOM methods may be more efficient than the NRF method for the computation of various nonlinear spectroscopic signals.

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“…Polarization-dependent 2DES provides another way to identify different types of coherence and is more accessible to experimental implementation. It was first applied to enhance or eliminate specific peaks in the results of 2D infrared spectroscopy. − Soon afterward, the polarization rotation sequence (60°, −60°, 0°, 0°) was employed in 2DES to eliminate the main diagonal features and highlight the cross-peaks (CPs). , The goal is to investigate the intermolecular couplings of the Fenna–Matthews–Olson (FMO) complex and the overlapping transitions of the major light-harvesting complex of photosystem II (LHCII) . Another polarization sequence (45°, −45°, 90°, 0°), denoted as “double-crossed” (DC), was also used to isolate the intermolecular coherence features from the population signals and determine its lifetime in LHCII .…”

mentioning

confidence: 99%

Revealing Intermolecular Electronic and Vibronic Coherence with Polarization-Dependent Two-Dimensional Beating Maps

Leng

Yan

Zhu

et al. 2023

J. Phys. Chem. Lett.

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Two-dimensional electronic spectroscopy (2DES) has been widely employed as an efficient tool to reveal the impact of intermolecular electronic and/ or vibronic quantum coherence on excitation energy transfer in light-harvesting complexes. However, intramolecular vibrational coherence would also contribute to oscillating signals in 2D spectra, along with the intermolecular coherence signals that are directly related to energy transfer. In this work, the possibility of screening the vibrational coherence signals is explored through polarization-dependent 2DES. The all-parallel (AP) and double-crossed (DC) polarization-dependent two-dimensional rephasing spectra (2DRS) are simulated for a minimalist heterodimer model with vibrational coupling. By combining the DC-2DRS and the 2D beating maps, we demonstrate that the population and vibrational coherence signals can be largely suppressed, resulting in highlighted intermolecular electronic and vibronic coherence signals. Moreover, the AP-and DC-2DBMs show rather different patterns at the vibrational frequency, indicating a possible way to identify pure vibrational coherence.

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A polarization scheme that resolves cross-peaks with transient absorption and eliminates diagonal peaks in 2D spectroscopy

Cited by 24 publications

References 68 publications

Phycobilisome’s Exciton Transfer Efficiency Relies on an Energetic Funnel Driven by Chromophore–Linker Protein Interactions

Phycobilisome’s Exciton Transfer Efficiency Relies on an Energetic Funnel Driven by Chromophore–Linker Protein Interactions

Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

Revealing Intermolecular Electronic and Vibronic Coherence with Polarization-Dependent Two-Dimensional Beating Maps

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