David Paleček

Coherent Picosecond Exciton Dynamics in a Photosynthetic Reaction Center

Photosynthetic reaction centers convert sunlight into a transmembrane electrochemical potential difference, providing chemical energy to almost all life on earth. Light energy is efficiently transferred through chromophore cofactors to the sites, where charge separation occurs. We applied two-dimensional electronic spectroscopy to assess the role of coherences in the photoresponse of the bacterial reaction center of Rhodobacter sphaeroides. By controlling the polarization of the laser beams, we were able to assign unambiguously the oscillatory dynamics to electronic (intermolecular) coherences. The data show that these coherences are sustained for more than 1 ps, indicating that the protein coherently retains some excitation energy on this time scale. Our finding provides a mechanism for effective delocalization of the excitations on the picosecond time scale by electronic coherence, setting the stage for efficient charge separation.

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.

Two mechanisms for dissipation of excess light in monomeric and trimeric light-harvesting complexes

Oxygenic photoautotrophs require mechanisms for rapidly matching the level of chlorophyll excited states from light harvesting with the rate of electron transport from water to carbon dioxide. These photoprotective reactions prevent formation of reactive excited states and photoinhibition. The fastest response to excess illumination is the so-called non-photochemical quenching which, in higher plants, requires the luminal pH sensor PsbS and other yet unidentified components of the photosystem II antenna. Both trimeric light-harvesting complex II (LHCII) and monomeric LHC proteins have been indicated as site(s) of the heat-dissipative reactions. Different mechanisms have been proposed: energy transfer to a lutein quencher in trimers, formation of a zeaxanthin radical cation in monomers. Here, we report on the construction of a mutant lacking all monomeric LHC proteins but retaining LHCII trimers. Its non-photochemical quenching induction rate was substantially slower with respect to the wild type. A carotenoid radical cation signal was detected in the wild type, although it was lost in the mutant. We conclude that non-photochemical quenching is catalysed by two independent mechanisms, with the fastest activated response catalysed within monomeric LHC proteins depending on both zeaxanthin and lutein and on the formation of a radical cation. Trimeric LHCII was responsible for the slowly activated quenching component whereas inclusion in supercomplexes was not required. This latter activity does not depend on lutein nor on charge transfer events, whereas zeaxanthin was essential.

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 (∼13 nm) at 20 kHz. We measure a photon flux of up to 4.4 × 10(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.

Quantum coherence as a witness of vibronically hot energy transfer in bacterial reaction center

Observation of coherence shifts reveals hot energy transfer and excess energy dissipation mechanisms in photosynthesis. Photosynthetic proteins have evolved over billions of years so as to undergo optimal energy transfer to the sites of charge separation. On the basis of spectroscopically detected quantum coherences, it has been suggested that this energy transfer is partially wavelike. This conclusion depends critically on the assignment of the coherences to the evolution of excitonic superpositions. We demonstrate that, for a bacterial reaction center protein, 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 the appearance of these coherences arises from a release of electronic energy during energy transfer. Our results establish how energy migrates on vibrationally hot chromophores in the reaction center, and they call for a reexamination of claims of quantum energy transfer in photosynthesis.

Sub-cycle ionization dynamics revealed by trajectory resolved, elliptically-driven high-order harmonic generation

The sub-cycle dynamics of electrons driven by strong laser fields is central to the emerging field of attosecond science. We demonstrate how the dynamics can be probed through high-order harmonic generation, where different trajectories leading to the same harmonic order are initiated at different times, thereby probing different field strengths. We find large differences between the trajectories with respect to both their sensitivity to driving field ellipticity and resonant enhancement. To accurately describe the ellipticity dependence of the long trajectory harmonics we must include a sub-cycle change of the initial velocity distribution of the electron and its excursion time. The resonant enhancement is observed only for the long trajectory contribution of a particular harmonic when a window resonance in argon, which is off-resonant in the field-free case, is shifted into resonance due to a large dynamic Stark shift.

Spatially and spectrally resolved quantum path interference with chirped driving pulses

We measure spectrally and spatially resolved high-order harmonics generated in argon using chirped multi-cycle laser pulses. Using a stable, high-repetition rate laser we observe detailed interference structures in the far-field. The structures are of two kinds; off-axis interference from the long trajectory only and on-axis interference including the short and long trajectories. The former is readily visible in the far-field spectrum, modulating both the spectral and spatial profile. To access the latter, we vary the chirp of the fundamental, imparting different phases on the different trajectories, thereby changing their relative phase. Using this method together with an analytical model, we are able to explain the on-axis behaviour and access the dipole phase parameters for the short (\(\alpha_s\)) and long (\(\alpha_l\)) trajectories. The extracted results compare very well with phase parameters calculated by solving the time-dependent Schrodinger equation. Going beyond the analytical model, we are also able to successfully reproduce the off-axis interference structure.

Low-temperature spectroscopy of bacteriochlorophyll c aggregates

Chlorosomes from green photosynthetic bacteria belong to the most effective light-harvesting antennas found in nature. Quinones incorporated in bacterichlorophyll (BChl) c aggregates inside chlorosomes play an important redox-dependent photo-protection role against oxidative damage of bacterial reaction centers. Artificial BChl c aggregates with and without quinones were prepared. We applied hole-burning spectroscopy and steady-state absorption and emission techniques at 1.9 K and two different redox potentials to investigate the role of quinones and redox potential on BChl c aggregates at low temperatures. We show that quinones quench the excitation energy in a similar manner as at room temperature, yet the quenching process is not as efficient as for chlorosomes. Interestingly, our data suggest that excitation quenching partially proceeds from higher excitonic states competing with ultrafast exciton relaxation. Moreover, we obtained structure-related parameters such as reorganization energies and inhomogeneous broadening of the lowest excited state, providing experimental ground for theoretical studies aiming at designing plausible large-scale model for BChl c aggregates including disorder.

Coherence shift to the ground state; a photoprocess explaining long-lived coherences in reaction centers

Long-lived coherences have been observed in various biological complexes and their origin is debated. We used polarization-controlled 2D electronic spectroscopy to reveal a photophysical process of coherence shift, explaining coherences in bacterial reaction centers.

High-Order Harmonic Generation and Plasmonics

Attosecond pulses allow for imaging of very fast processes, like electron dynamics. Stockman et al. suggested to use these pulses in connection with a Photoemission electron microscope (PEEM) to study the ultrafast dynamics of plasmons (Stockman et al. Nat Photonics 1:539–544, 2007). For efficient plasmon studies, the repetition rate of the attosecond pulses used needs to be higher than a few kHz (Mikkelsen et al. Rev Sci Instrum 80:123703, 2009). Attosecond pulses are produced in a process called high-order harmonic generation (HHG) (Paul et al. Science 292(5522):1689–1692, 2001; Ferray et al. J Phys B At Mol Opt Phys 21:L31–L35, 1988). In HHG, a strong laser field allows an electron to tunnel out, get accelerated and recombine with a high kinetic energy resulting in extreme ultraviolet attosecond pulses. The large intensity needed to drive the process normally limits the repetition rate of the laser to a few kHz. Using a tight focusing scheme (Heyl et al. Phys Rev Lett 107:033903, 2011; Vernaleken et al. Opt Lett 36:3428–3430, 2011), we, however, generate harmonics at a repetition rate of 200 kHz, both with a commercial turn-key laser and with an advanced laser system. Suitable nanostructures for a strong field enhancement are produced in-house and the field enhancement is studied with PEEM in a non-time resolved manner. With high-order harmonics produced at a high repetition rate, we hope to be able to follow also the ultrafast dynamics of plasmons in these structures (Marsell et al. Ann der Phys 525:162–170, 2013).