Quantum Coherence as a Witness of Vibronically Hot Energy Transfer in Bacterial Reaction Centre

Photosynthetic proteins have evolved over billions of years so as to undergo optimal energy transfer to the sites of charge separation. Based on spectroscopically detected quantum coherences, it has been suggested that this energy transfer is partially wavelike. This conclusion critically depends on assignment of the coherences to the evolution of excitonic superpositions. Here we demonstrate for a bacterial reaction centre protein that long-lived coherent spectroscopic oscillations, which bear canonical signatures of excitonic superpositions, are essentially vibrational excited state coherences shifted to the ground state of the chromophores . We show that appearance of these coherences is brought about by release of electronic energy during the energy transfer. Our results establish how energy migrates on vibrationally hot chromophores in the reaction centre and they call for a re-examination of claims of quantum energy transfer in photosynthesis

Vliv redoxního stavu na zhášení excitace v bakteriochlorofylových agregátech

Využitím pouhých 4 % sluneční energie dopadajících na Zemi by bylo možno pokrýt současnou energetickou spotřebu lidstva. Vhodným světlosběrným sys- témem sloužícím jako inspirace pro vývoj umělé fotosyntézy se zdají být chlo- rosomy zelených sirných bakterií. V této práci byly porovnány absorpční a hole burningová spektra uměle připravených agregátů podobných chlorosomům s růz- ným složením, s cílem ověřit roli chinonů při zhášení excitace v těchto agregátech a prozkoumat jeho redoxní závislost. Absorpční spektra za pokojové a heliové teploty ukázala na podobnost umělých agregátů s chlorosomy. Hole burnigový experiment potvrdil předpokládanou roli chinonů při zhášení excitace za ae- robních podmínek. Na druhou stranu, za anaerobních podmínek bylo pozo- rováno ještě výraznější zhášení excitace pro některé vlnové délky. Výrazné vy- lepšení původní aparatury umožnilo získat kvalitnější experimentální data, která nastínila mnoho nových otázek, na které stojí za to se pokusit najít v budoucnu odpovědi.Harvesting only 4 % of light striking the Earth could possibly fulfill present energy demands of a mankind. Chlorosome of green sulfur bacteria is re- garded as suitable light-harvesting system for photosynthesis imitation. This work presents comparison of absorption and hole burning spectra of artificially prepared aggregates similar to chlorosomes with different compositions in order to verify the proposed role of quinones in excitation quenching and its redox de- pendence. Absorption spectra at room and helium temperature showed a resem- blance between artificial aggregates and chlorosomes. Hole burning experiments verified the role of quinones in excitation quenching under aerobic conditions. Even more pronounced excitation quenching was observed under anaerobic con- ditions. Significant improvements of the original experimental set-up provided better experimental data which raised many further question that are worth trying to answer in the future.Katedra chemické fyziky a optikyDepartment of Chemical Physics and OpticsMatematicko-fyzikální fakultaFaculty of Mathematics and Physic

High-order harmonic generation using a high-repetition-rate turnkey laser

We generate high-order harmonics at high pulse repetition rates using a turnkey laser. High-order harmonics at 400 kHz are observed when argon is used as target gas. In neon we achieve generation of photons with energies exceeding 90 eV ($\sim$13 nm) at 20 kHz. We measure a photon flux of 4.4$\cdot10^{10}$ photons per second per harmonic in argon at 100 kHz. Many experiments employing high-order harmonics would benefit from higher repetition rates, and the user-friendly operation opens up for applications of coherent extreme ultra-violet pulses in new research areas

Revealing vibronic coupling in chlorophyll c1 by polarization-controlled 2D electronic spectroscopy

Vibronic coupling between molecules has been recently discussed to play an important role in photosynthetic functions. Furthermore, this type of coupling between electronic states has been suggested to define photophysical properties of chlorophylls, a family of photosynthetic molecules. However, experimental investigation of vibronic coupling presents a major challenge. One subtle way to study vibronic coupling is by excitation and observation of superpositions of vibrational states via transitions to vibronically mixed states. Such superpositions, called coherences, are then observed as quantum beats in non-linear spectroscopy experiments. Here we present polarization-controlled two-dimensional electronic spectroscopy study of the chlorophyll c1 molecule at cryogenic (77 K) temperature. By applying complex analysis to the oscillatory signals we are able to unravel vibronic coupling in this molecule. The vibronic mixing picture that we see is much more complex than was thought before

Vibronic origin of long-lived coherence in an artificial molecular light harvester

Natural and artificial light harvesting processes have recently gained new interest. Signatures of long lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically aligned tubular system, polarization controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence

Long-lived and disorder-free charge transfer states enable endothermic charge separation in efficient non-fullerene organic solar cells

Funder: HKU | University Research Committee, University of Hong Kong (HKU Research Committee); doi: https://doi.org/10.13039/501100003802Abstract: Organic solar cells based on non-fullerene acceptors can show high charge generation yields despite near-zero donor–acceptor energy offsets to drive charge separation and overcome the mutual Coulomb attraction between electron and hole. Here, we use time-resolved optical spectroscopy to show that free charges in these systems are generated by thermally activated dissociation of interfacial charge-transfer states that occurs over hundreds of picoseconds at room temperature, three orders of magnitude slower than comparable fullerene-based systems. Upon free electron–hole encounters at later times, both charge-transfer states and emissive excitons are regenerated, thus setting up an equilibrium between excitons, charge-transfer states and free charges. Our results suggest that the formation of long-lived and disorder-free charge-transfer states in these systems enables them to operate closely to quasi-thermodynamic conditions with no requirement for energy offsets to drive interfacial charge separation and achieve suppressed non-radiative recombination

Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization.

Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10-2 cm2/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm2/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions

Sensitization of lamina I spinoparabrachial neurons parallels heat hyperalgesia in the chronic constriction injury model of neuropathic pain

It has been proposed that spinal lamina I neurons with ascending axons that project to the midbrain play a crucial role in hyperalgesia. To test this hypothesis the quantitative properties of lamina I spinoparabrachial neurons in the chronic constriction injury (CCI) model of neuropathic pain were compared to those of unoperated and sham-operated controls. Behavioural testing showed that animals with a CCI exhibited heat hyperalgesia within 4 days of the injury, and this hyperalgesia persisted throughout the 14-day post-operative testing period. In the CCI, nociceptive lamina I spinoparabrachial neurons had heat thresholds that were significantly lower than controls (43.0 ± 2.8°C vs. 46.7 ± 2.6°C; P < 10−4, ANOVA). Nociceptive lamina I spinoparabrachial neurons were also significantly more responsive to graded heat stimuli in the CCI, compared to controls (P < 0.02, 2-factor repeated-measures ANOVA), and increased after-discharges were also observed. Furthermore, the heat-evoked stimulus–response functions of lamina I spinoparabrachial neurons in CCI animals co-varied significantly (P < 0.03, ANCOVA) with the amplitude of heat hyperalgesia determined behaviourally. Taken together these results are consistent with the hypothesis that lamina I spinoparabrachial neurons have an important mechanistic role in the pathophysiology of neuropathic pain

Genotyping a second growth coast redwood forest : a high throughput methodology

The idea that excitonic (electronic) coherences are of fundamental importance to natural photosynthesis gained popularity when slowly dephasing quantum beats (QBs) were observed in the two-dimensional electronic spectra of the Fenna–Matthews–Olson (FMO) complex at 77 K. These were assigned to superpositions of excitonic states, a controversial interpretation, as the strong chromophore–environment interactions in the complex suggest fast dephasing. Although it has been pointed out that vibrational motion produces similar spectral signatures, a concrete assignment of these oscillatory signals to distinct physical processes is still lacking. Here we revisit the coherence dynamics of the FMO complex using polarization-controlled two-dimensional electronic spectroscopy, supported by theoretical modelling. We show that the long-lived QBs are exclusively vibrational in origin, whereas the dephasing of the electronic coherences is completed within 240 fs even at 77 K. We further find that specific vibrational coherences are produced via vibronically coupled excited states. The presence of such states suggests that vibronic coupling is relevant for photosynthetic energy transfer

Vliv redoxního stavu na zhášení excitace v bakteriochlorofylových agregátech

Harvesting only 4 % of light striking the Earth could possibly fulfill present energy demands of a mankind. Chlorosome of green sulfur bacteria is re- garded as suitable light-harvesting system for photosynthesis imitation. This work presents comparison of absorption and hole burning spectra of artificially prepared aggregates similar to chlorosomes with different compositions in order to verify the proposed role of quinones in excitation quenching and its redox de- pendence. Absorption spectra at room and helium temperature showed a resem- blance between artificial aggregates and chlorosomes. Hole burning experiments verified the role of quinones in excitation quenching under aerobic conditions. Even more pronounced excitation quenching was observed under anaerobic con- ditions. Significant improvements of the original experimental set-up provided better experimental data which raised many further question that are worth trying to answer in the future