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Fleming, Graham R.

Publications and source records attributed to Fleming, Graham R..

32 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Synthetic Control of Exciton Dynamics in Bioinspired Cofacial Porphyrin Dimers

Understanding how the complex interplay among excitonic interactions, vibronic couplings, and reorganization energy determines coherence-enabled transport mechanisms is a grand challenge with both foundational implications and potential payoffs for energy science. We use a combined experimental and theoretical approach to show how a modest change in structure may be used to modify the exciton delocalization, tune electronic and vibrational coherences, and alter the mechanism of exciton transfer in covalently linked cofacial Zn-porphyrin dimers (meso-beta linked AB m-β and meso-meso linked AA m-m ). While both AB m-β and AA m-m feature zinc porphyrins linked by a 1,2-phenylene bridge, differences in the interporphyrin connectivity set the lateral shift between macrocycles, reducing electronic coupling in AB m-β and resulting in a localized exciton. Pump-probe experiments show that the exciton dynamics is faster by almost an order of magnitude in the strongly coupled AA m-m dimer, and two-dimensional electronic spectroscopy (2DES) identifies a vibronic coherence that is absent in AB m-β . Theoretical studies indicate how the interchromophore interactions in these structures, and their system-bath couplings, influence excitonic delocalization and vibronic coherence-enabled rapid exciton transport dynamics. Real-time path integral calculations reproduce the exciton transfer kinetics observed experimentally and find that the linking-modulated exciton delocalization strongly enhances the contribution of vibronic coherences to the exciton transfer mechanism, and that this coherence accelerates the exciton transfer dynamics. These benchmark molecular design, 2DES, and theoretical studies provide a foundation for directed explorations of nonclassical effects on exciton dynamics in multiporphyrin assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Vibronic coupling in light-harvesting complex II revisited

A growing body of work has pointed to vibronic mixing as a crucial design principle for efficient energy and charge transfer in natural and artificial systems.= Notable among these studies was the recent observation of vibronically promoted ultrafast energy flow in the major antenna complex of green plants and algae light-harvesting complex II (LHCII)—the most abundant membrane protein on the Earth—via the emerging experimental technique two-dimensional electronic-vibrational (2DEV) spectroscopy. This spectroscopy, which correlates electronic and nuclear degrees-of-freedom, shows promise for providing mechanistic insight into vibronic coupling; however, explicit theoretical input is necessary to extract such a detail. In a separate paper, we have developed a heterodimer model that describes various forms of vibronic coupling—which were speculated to be present in LHCII—resulting from diagonal electron–phonon coupling giving Franck–Condon (FC) activity and the nuclear dependence of the electronic transition dipole moment giving Herzberg–Teller (HT) activity. Here, we draw connections between this theoretical work and recent experimental studies in order to demonstrate how HT activity is leveraged in the function of LHCII.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Vibronic coupling in energy transfer dynamics and two-dimensional electronic–vibrational spectra

We introduce a heterodimer model in which multiple mechanisms of vibronic coupling and their impact on energy transfer can be explicitly studied. We consider vibronic coupling that arises through either Franck-Condon activity in which each site in the heterodimer has a local electron-phonon coupling or Herzberg-Teller activity in which the transition dipole moment coupling the sites has an explicit vibrational mode-dependence. We have computed two-dimensional electronic-vibrational (2DEV) spectra for this model while varying the magnitude of these two effects and find that 2DEV spectra contain static and dynamic signatures of both types of vibronic coupling. Franck-Condon activity emerges through a change in the observed excitonic structure, while Herzberg-Teller activity is evident in the appearance of significant side-band transitions that mimic the lower-energy excitonic structure. A comparison of quantum beating patterns obtained from analysis of the simulated 2DEV spectra shows that this technique can report on the mechanism of energy transfer, elucidating a means of experimentally determining the role of specific vibronic coupling mechanisms in such processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Two-dimensional electronic–vibrational spectroscopy: Exploring the interplay of electrons and nuclei in excited state molecular dynamics

Two-dimensional electronic-vibrational spectroscopy (2DEVS) is an emerging spectroscopic technique which exploits two different frequency ranges for the excitation (visible) and detection (infrared) axes of a 2D spectrum. In contrast to degenerate 2D techniques, such as 2D electronic or 2D infrared spectroscopy, the spectral features of a 2DEV spectrum report cross correlations between fluctuating electronic and vibrational energy gaps rather than autocorrelations as in the degenerate spectroscopies. The center line slope of the spectral features reports on this cross correlation function directly and can reveal specific electronic-vibrational couplings and rapid changes in the electronic structure, for example. The involvement of the two types of transition moments, visible and infrared, makes 2DEVS very sensitive to electronic and vibronic mixing. 2DEV spectra also feature improved spectral resolution, making the method valuable for unraveling the highly congested spectra of molecular complexes. The unique features of 2DEVS are illustrated in this paper with specific examples and their origin described at an intuitive level with references to formal derivations provided. Although early in its development and far from fully explored, 2DEVS has already proven to be a valuable addition to the tool box of ultrafast nonlinear optical spectroscopy and is of promising potential in future efforts to explore the intricate connection between electronic and vibrational nuclear degrees of freedom in energy and charge transport applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electron–Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer

Although photoinduced proton-coupled electron transfer (PCET) plays an essential role in photosynthesis, a full understanding of the mechanism is still lacking due to the complex nonequilibrium dynamics arising from the strongly coupled electronic and nuclear degrees of freedom. Here we report the photoinduced PCET dynamics of a biomimetic model system investigated by means of transient IR and two-dimensional electronic–vibrational (2DEV) spectroscopies, IR spectroelectrochemistry (IRSEC), and calculations utilizing long-range-corrected hybrid density functionals. This collective experimental and theoretical effort provides a nuanced picture of the complicated dynamics and synergistic motions involved in photoinduced PCET. In particular, the evolution of the 2DEV line shape, which is highly sensitive to the mixing of vibronic states, is interpreted by accurate computational modeling of the charge separated state and is shown to represent a gradual change in electron density distribution associated with a dihedral twist that occurs on a 120 fs time scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The role of mixed vibronic Q y -Q x states in green light absorption of light-harvesting complex II

The importance of green light for driving natural photosynthesis has long been underappreciated, however, under the presence of strong illumination, green light actually drives photosynthesis more efficiently than red light. This green light is absorbed by mixed vibronic Q y -Q x states, arising from chlorophyll (Chl)-Chl interactions, although almost nothing is known about these states. Here, we employ polarization-dependent two-dimensional electronic-vibrational spectroscopy to study the origin and dynamics of the mixed vibronic Q y -Q x states of light-harvesting complex II. We show the states in this region dominantly arise from Chl b and demonstrate how it is possible to distinguish between the degree of vibronic Q y versus Q x character. We find that the dynamics for states of predominately Chl b Q y versus Chl b Q x character are markedly different, as excitation persists for significantly longer in the Q x states and there is an oscillatory component to the Q x dynamics, which will be discussed. Our findings demonstrate the central role of electronic-nuclear mixing in efficient light-harvesting and the different functionalities of Chl a and Chl b .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Variable optical properties of light-harvesting complex II revisited

Understanding photosynthetic light harvesting requires knowledge of the molecular mechanisms that dissipate excess energy in thylakoids. However, it remains unclear how the physical environment of light-harvesting complex II (LHCII) influences the process of chlorophyll de-excitation. Here, we demonstrate that protein-protein interactions between LHCIIs affect the optical properties of LHCII and thus influence the total energy budget. Aggregation of LHCII in the dark altered its absorption properties, independent of the amount of prior light exposure. We also revisited the triplet excited state involved in light-induced fluorescence quenching and found another relaxation pathway involving emission in the green region, which might be related to triplet excited energy transfer to neighboring carotenoids and annihilation processes that result in photoluminescence. LHCII- containing liposomes with different protein densities exhibited altered fluorescence and scattering properties. Our results suggest that macromolecular reorganization affects overall optical properties, which need to be addressed to compare the level of energy dissipation.

Iwai, Masakazu↗
DOE OSTI2020

Quantum Ratcheted Photophysics in Energy Transport

In this paper, we explore the scope of vibrations as quantum ratchets that serve as nonthermal routes to achieving population transport in systems where excitation transport between molecules is otherwise energetically unfavorable. In addition to their role as channels of transport, we investigate the effect of resonance of the vibrations, which are described by Huang-Rhys mixing, with excitonic energy gaps, which leads to strongly mixed vibronic excitons. Finally, we explore the interplay of resonance and Huang-Rhys mixing with electronic coupling between the molecules, in the presence of a dissipative bath, in optimizing transport in such systems. Furthermore, we find that while resonance is desirable, a moderate electronic coupling has a stronger positive effect in contrast to a large electronic coupling, which results in delocalized excitations across molecules and hampers unidirectional transport. We also report a special resonance regime that is able to circumvent the transport problems arising from large electronic couplings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The role of resonant nuclear modes in vibrationally assisted energy transport: The LHCII complex

In this paper, we discuss the explicit role of resonant nuclear/vibrational modes in mediating energy transport among chlorophylls in the Light-harvesting Complex II (LHCII), the major light-harvesting complex in green plants. The vibrational modes are considered to be resonant/quasi-resonant with the energy gap between electronic excitons. These resonant vibrations, along with the remaining nuclear degrees of freedom, constitute the environment/bath to the electronically excited system and contribute to two major phenomena: (a) decoherence and (b) incoherent phonon-mediated population relaxation. In this work, we explore the subtle interplay among the electronic excitation, the resonant vibrations, and the environment in dictating environment assisted quantum transport in light-harvesting complexes. We conclusively show that resonant vibrations are capable of boosting the incoherent population relaxation pathways and cause rapid decoherence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Solvent Mediated Excited State Proton Transfer in Indigo Carmine

Excited state proton transfer (ESPT) is thought to be responsible for the photostability of biological molecules, including DNA and proteins, and natural dyes such as indigo. However, the mechanistic role of the solvent interaction in driving ESPT is not well understood. Here, the electronic excited state deactivation dynamics of indigo carmine (InC) is mapped by visible pump-infrared probe and two-dimensional electronic-vibrational (2DEV) spectroscopy and complemented by electronic structure calculations. The observed dynamics reveal notable differences between InC in a protic solvent, D$_2$O , and an aprotic solvent, deuterated dimethyl sulfoxide (dDMSO). Notably, an acceleration in the excited state decay is observed in D$_2$O (<10 ps) compared to dDMSO (130 ps). Our data reveals clear evidence for ESPT in D$_2$O accompanied by a significant change in dipole moment, which is found not to occur in dDMSO. We conclude that the ability of protic solvents to form intermolecular H-bonds with InC enables ESPT, which facilitates a rapid nonradiative S$_1$ → S$_0$ transition via the monoenol intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Lineshape characterization of excitons in monolayer WS 2 by two-dimensional electronic spectroscopy

The optical properties of monolayer transition metal dichalcogenides (TMDCs), an important family of two-dimensional (2D) semiconductors for optoelectronic applications, are dominated by two excitons A (XA) and B (XB) located at K/K's valleys. The lineshape of the excitons is an indicator of the interaction of the excitons with other particles and also largely determines the performance of TMDC-based optoelectronic devices. In this work, we apply 2D electronic spectroscopy (2DES), which enables separation of the intrinsic homogeneous linewidth and the extrinsic inhomogeneous linewidth, to dissect the lineshape of XA in monolayer WS 2 . With a home-built broadband optical parametric amplifier, the 2D spectra give the exciton linewidth values for extensive ranges of excitation densities and temperatures, reflecting inter-exciton and exciton–phonon interactions. Meanwhile, the time-domain evolution of the lineshape reveals a similar rate of spectral diffusion to that in quantum wells (QWs) based on III–V semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2020

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

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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