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Register a new userIntramolecular Vibrations Complement the Robustness of Primary Charge Separation in a Dimer Model of the Photosystem II Reaction Center
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The energy conversion of oxygenic photosynthesis is triggered by primary charge separation in proteins at the photosystem II reaction center. Here, we investigate the impacts of the protein environment and intramolecular vibrations on primary charge separation at the photosystem II reaction center. This is accomplished by combining the quantum dynamic theories of condensed phase electron transfer with quantum chemical calculations to evaluate the vibrational Huang-Rhys factors of chlorophyll and pheophytin molecules. We report that individual vibrational modes play a minor role in promoting the charge separation, contrary to the discussion in recent publications. Nevertheless, these small contributions accumulate to considerably influence the charge separation rate, resulting in sub-picosecond charge separation almost independent of the driving force and temperature. We suggest that the intramolecular vibrations complement the robustness of the charge separation in the photosystem II reaction center against the inherently large static disorder of the involved electronic energies.
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The photosystem II reaction centre is the photosynthetic complex responsible for oxygen production on Earth. Its water splitting function is particularly favoured by the formation of a stable charge separated state via a pathway that starts at an accessory chlorophyll. Here we envision a photovoltaic device that places one of these complexes between electrodes and investigate how the mean current and its fluctuations depend on the microscopic interactions underlying charge separation in the pathway considered. Our results indicate that coupling to well resolved vibrational modes does not necessarily offer an advantage in terms of power output but can lead to photo-currents with suppressed noise levels characterizing a multi-step ordered transport process. Besides giving insight into the suitability of these complexes for molecular-scale photovoltaics, our work suggests a new possible biological function for the vibrational environment of photosynthetic reaction centres, namely, to reduce the intrinsic current noise for regulatory processes.
Photosystem II is crucial for life on Earth as it provides oxygen as a result of photoinduced electron transfer and water splitting reactions. The excited state dynamics of the photosystem II-reaction center (PSII-RC) has been a matter of vivid debate because the absorption spectra of the embedded chromophores significantly overlap and hence it is extremely difficult to distinguish transients. Here, we report the two-dimensional electronic-vibrational spectroscopic study of the PSII-RC. The simultaneous resolution along both the visible excitation and infrared detection axis is crucial in allowing for the character of the excitonic states and interplay between them to be clearly distinguished. In particular, this work demonstrates that the mixed exciton-charge transfer state, previously proposed to be responsible for the far-red light operation of photosynthesis, is characterized by the Chl$_{rm D1}^+$Phe$^-$ radical pair and can be directly prepared upon photoexcitation. Further, we find that the initial electron acceptor in the PSII-RC is Phe, rather than P$_{rm D1}$, regardless of excitation wavelength.
Density-functional tight binding (DFTB) has become a popular form of approximate density-functional theory (DFT) based upon a minimal valence basis set and neglect of all but two center integrals. We report the results of our tests of a recent long-range correction (lc) for time-dependent (TD) lc-DFTB by carrying out TD-lc-DFTB fewest switches surface hopping (FSSH) calculations of energy and charge transfer times using the relatively new DFTBaby program. An advantage of this method is the ability to run enough trajectories to get meaningful ensemble averages. Our interest in the present work is less in determining exact energy and charge transfer rates than in understanding how the results of these calculations vary with the value of the range-separation parameter (Rlc = 1/{mu}) for a model organic solar cell heterojunction consisting of a van der Waals complex P/F made up of single pentacene (P) molecule together with a single buckminsterfullerene (F) molecule. The default value of Rlc = 3.03 a0 is found to be much too small as neither energy nor charge transfer is observed until Rlc ~ 10 a0. Tests at a single geometry show that best agreement with high-quality ab-initio spectra is obtained in the limit of no lc (i.e., very large Rlc.) A plot of energy and charge transfer rates as a function of Rlc is provided which suggests that a value of Rlc ~ 15 a0 yields the typical literature charge transfer time of about 100 fs. However, energy and charge transfer times become as high as ~ 300 fs for Rlc ~ 25 a0. A closer examination of the charge transfer process P*/F to P+/F- shows that the initial electron transfer is accompanied by a partial delocalization of the P hole onto F which then relocalizes back onto P, consistent with a polaron-like picture in which the nuclei relax to stabilize the resultant redistribution of charges.
The H + D_2^+(v=0,1 and 2) charge transfer reaction is studied using an accurate wave packet method, using recently proposed coupled diabatic potential energy surfaces. The state-to-state cross section is obtained for three different channels: non-reactive charge transfer, reactive charge transfer, and exchange reaction. The three processes proceed via the electronic transition from the first excited to the ground electronic state. The cross section for the three processes increases with the initial vibrational excitation. The non-reactive charge transfer process is the dominant channel, whose branching ratio increases with collision energy, and it compares well with experimental measurements at collision energies around 0.5 eV. For lower energies the experimental cross section is considerably higher, suggesting that it corresponds to higher vibrational excitation of D_2^+(v) reactants. Further experimental studies of this reaction and isotopic variants are needed, where conditions are controlled to obtain a better analysis of the vibrational effects of the D_2^+ reagents.
We extract the dynamics implicit in an algebraic fitted model Hamiltonian for the hydrogen chromophores vibrational motion in the molecule $CF_3CHFI$. The original model has 4 degrees of freedom, three positions and one representing interbond couplings. A conserved polyad allows the reduction to 3 degrees of freedom. For most quantum states we can identify the underlying motion that when quantized gives the said state. Most of the classifications, identifications and assignments are done by visual inspection of the already available wave function semiclassically transformed from the number representation to a representation on the reduced dimension toroidal configuration space corresponding to the classical action and angle variables. The concentration of the wave function density to lower dimensional subsets centered on idealized simple lower dimensional organizing structures and the behavior of the phase along such organizing centers already reveals the atomic motion. Extremely little computational work is needed.
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