A General control mechanism of energy flow in the excited state of polyenic biochromophores.

Quantum dynamics in photobiology is a highly controversial subject of modern research. In particular, the role of low-frequency vibrational coherence of biochromophores has been intensely discussed. Coherent control of polyenic chromophores, like carotenoids and retinoids, has been showing that the manipulation of such low frequency coherences may play a crucial role in the evolution of excited population and therefore in the efficiency of photosynthesis. However, no precise control mechanism has been derived. In order to clarify this open question, we combined quantum dynamical modelling with a sensitive experimental technique, namely Pump-Degenerate Four Wave Mixing (Pump-DFWM). In this work we investigate in detail the internal conversion channel of β-carotene, an important polyenic chromophore, under multipulse excitation and focus on the role of the non-adiabatic coupling between excited-state potentials and the internal energy loss. Our control mechanism is based on the interference between wavepackets in the excited state, which leads to a transient evolution of the vibrational population dependent on the relative phase between excitation sub-pulses. Such a transient evolution can affect the branching ratio between competing channels in the excited state. Therefore, our results are able to rationalize pulse shapes found in a whole class of coherent control experiments involving polyenic biochromophores, like in light harvesting complexes and in bacteriorhodopsin

Quantum-coherent dynamics in photosynthetic charge separation revealed by wavelet analysis

Experimental/theoretical evidence for sustained vibration-assisted electronic (vibronic) coherence in the Photosystem II Reaction Center (PSII RC) indicates that photosynthetic solar-energy conversion might be optimized through the interplay of electronic and vibrational quantum dynamics. This evidence has been obtained by investigating the primary charge separation process in the PSII RC by two-dimensional electronic spectroscopy (2DES) and Redfield modeling of the experimental data. However, while conventional Fourier transform analysis of the 2DES data allows oscillatory signatures of vibronic coherence to be identified in the frequency domain in the form of static 2D frequency maps, the real-time evolution of the coherences is lost. Here we apply for the first time wavelet analysis to the PSII RC 2DES data to obtain time-resolved 2D frequency maps. These maps allow us to demonstrate that i) coherence between the excitons initiating the two different charge separation pathways is active for more than 500 fs, and ii) coherence between exciton and charge-transfer states, the reactant and product of the charge separation reaction, respectively, is active for at least 1 ps. These findings imply that the PSII RC employs coherence i) to sample competing electron transfer pathways, and ii) to perform directed, ultrafast and efficient electron transfer.Comment: Scientific reports 201

Long-lived quantum coherence in photosynthetic complexes at physiological temperature

Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center which stores energy from the photon in chemical bonds. This process occurs with near-perfect quantum efficiency. Recent experiments at cryogenic temperatures have revealed that coherent energy transfer - a wavelike transfer mechanism - occurs in many photosynthetic pigment-protein complexes (1-4). Using the Fenna-Matthews-Olson antenna complex (FMO) as a model system, theoretical studies incorporating both incoherent and coherent transfer as well as thermal dephasing predict that environmentally assisted quantum transfer efficiency peaks near physiological temperature; these studies further show that this process is equivalent to a quantum random walk algorithm (5-8). This theory requires long-lived quantum coherence at room temperature, which never has been observed in FMO. Here we present the first evidence that quantum coherence survives in FMO at physiological temperature for at least 300 fs, long enough to perform a rudimentary quantum computational operation. This data proves that the wave-like energy transfer process discovered at 77 K is directly relevant to biological function. Microscopically, we attribute this long coherence lifetime to correlated motions within the protein matrix encapsulating the chromophores, and we find that the degree of protection afforded by the protein appears constant between 77 K and 277 K. The protein shapes the energy landscape and mediates an efficient energy transfer despite thermal fluctuations. The persistence of quantum coherence in a dynamic, disordered system under these conditions suggests a new biomimetic strategy for designing dedicated quantum computational devices that can operate at high temperature.Comment: PDF files, 15 pages, 3 figures (included in the PDF file

Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution

The interaction of the monomeric chlorophyll Q-band electronic transition with solvents of differing physical-chemical properties is investigated through two-dimensional electronic spectroscopy (2DES). Chlorophyll constitutes the key chromophore molecule in light harvesting complexes. It is well-known that the surrounding protein in the light harvesting complex fine-tunes chlorophyll electronic transitions to optimize energy transfer. Therefore, an understanding of the influence of the environment on the monomeric chlorophyll electronic transitions is important. The Q-band 2DES is inhomogeneous at early times, particularly in hydrogen bonding polar solvents, but also in nonpolar solvents like cyclohexane. Interestingly this inhomogeneity persists for long times, even up to the nanosecond time scale in some solvents. The reshaping of the 2DES occurs over multiple time scales and was assigned mainly to spectral diffusion. At early times the reshaping is Gaussian-like, hinting at a strong solvent reorganization effect. The temporal evolution of the 2DES response was analyzed in terms of a Brownian oscillator model. The spectral densities underpinning the Brownian oscillator fitting were recovered for the different solvents. The absorption spectra and Stokes shift were also properly described by this model. The extent and nature of inhomogeneous broadening was a strong function of solvent, being larger in H-bonding and viscous media and smaller in nonpolar solvents. The fastest spectral reshaping components were assigned to solvent dynamics, modified by interactions with the solute

Selected bibliography on the modeling and control of plant processes

A bibliography of information pertinent to the problem of simulating plants is presented. Detailed simulations of constituent pieces are necessary to justify simple models which may be used for analysis. Thus, this area of study is necessary to support the Earth Resources Program. The report sums up the present state of the problem of simulating vegetation. This area holds the hope of major benefits to mankind through understanding the ecology of a region and in improving agricultural yield