319 research outputs found
Mixing of exciton and charge-transfer states in Photosystem II reaction centers: Modeling of stark spectra with modified redfield theory
AbstractWe propose an exciton model for the Photosystem II reaction center (RC) based on a quantitative simultaneous fit of the absorption, linear dichroism, circular dichroism, steady-state fluorescence, triplet-minus-singlet, and Stark spectra together with the spectra of pheophytin-modified RCs, and so-called RC5 complexes that lack one of the peripheral chlorophylls. In this model, the excited state manifold includes a primary charge-transfer (CT) state that is supposed to be strongly mixed with the pure exciton states. We generalize the exciton theory of Stark spectra by 1), taking into account the coupling to a CT state (whose static dipole cannot be treated as a small parameter in contrast to usual excited states); and 2), expressing the line shape functions in terms of the modified Redfield approach (the same as used for modeling of the linear responses). This allows a consistent modeling of the whole set of experimental data using a unified physical picture. We show that the fluorescence and Stark spectra are extremely sensitive to the assignment of the primary CT state, its energy, and coupling to the excited states. The best fit of the data is obtained supposing that the initial charge separation occurs within the special-pair PD1PD2. Additionally, the scheme with primary electron transfer from the accessory chlorophyll to pheophytin gave a reasonable quantitative fit. We show that the effectiveness of these two pathways is strongly dependent on the realization of the energetic disorder. Supposing a mixed scheme of primary charge separation with a disorder-controlled competition of the two channels, we can explain the coexistence of fast sub-ps and slow ps components of the Phe-anion formation as revealed by different ultrafast spectroscopic techniques
Parametric Projection Operator Technique for Second Order Non-linear Response
We demonstrate the application of the recently introduced parametric
projector operator technique to a calculation of the second order non-linear
optical response of a multilevel molecular system. We derive a parametric
quantum master equation (QME) for the time evolution of the excited state of an
excitonic system after excitation by the first two pulses in the usual
spectroscopic four-wave-mixing scheme. This master equation differs from the
usual QME by a correction term which depends on the delay \tau between the
pulses. In the presence of environmental degrees of freedom with finite bath
correlation time and in the presence of intramolecular vibrations we find
distinct dynamics of both the excite state populations and the electronic
coherence for different delays \tau.Comment: 15 pages, 8 figure
Exciton delocalization in the antenna of purple bacteria: Exciton spectrum calculations using X-ray data and experimental site inhomogeneity
AbstractElectron absorption and circular dichroism spectra of the peripheral light-harvesting complex (LH2) of photosynthetic purple bacteria were calculated taking into account the real-life spatial arrangement and experimental inhomogeneous broadening of bacteriochlorophyll molecules. It was shown that strong excitonic interactions between 18 bacteriochlorophyll molecules (BChl850) within the circular aggregate of the LH2 complex result in an exciton delocalization over all these pigment molecules. The site inhomogeneity (spectral disorder) practically has no influence on exciton delocalization. The splitting between two lowest exciton levels corresponds to experimentally revealed splitting by hole-burning studies of the LH2 complex
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Dark states in the light-harvesting complex 2 revealed by two-dimensional electronic spectroscopy
Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy
Influence of Static and Dynamic Disorder on the Anisotropy of Emission in the Ring Antenna Subunits of Purple Bacteria Photosynthetic Systems
Using the reduced density matrix formalism the time dependence of the exciton
scattering in light-harvesting ring systems of purple bacteria is calculated.
In contrast to the work of Kumble and Hochstrasser (J. Chem. Phys. 109 (1998)
855) static disorder (fluctuations of the site energies) as well as dynamic
disorder (dissipation) is taken into account. For the description of
dissipation we use Redfield theory in exciton eigenstates without secular
approximation. This is shown to be equivalent to the Markovian limit of Capek's
theory in local states. Circular aggregates with 18 pigments are studied to
model the B850 ring of bacteriochlorophyls within LH2 complexes. It can be
demonstrated that the dissipation is important for the time-dependent
anisotropy of the fluorescence. Smaller values of static disorder are
sufficient to produce the same decay rates in the anisotropy in comparison with
the results by Kumble and Hochstrasser
Complete mapping of energy transfer pathways in the plant light-harvesting complex Lhca4
The Lhca4 antenna complex of plant Photosystem I (PSI) is characterized by extremely red-shifted and broadened absorption and emission bands from its low-energy chlorophylls (Chls). The mixing of a charge-transfer (CT) state with the excited state manifold causing these so-called red forms results in highly complicated multi-component excited energy transfer (EET) kinetics within the complex. The two-dimensional electronic spectroscopy experiments presented here reveal that EET towards the CT state occurs on three timescales: fast from the red Chls (within 1 ps), slower (5-7 ps) from the stromal side Chls, and very slow (100-200 ps) from a newly discovered 690 nm luminal trap. The excellent agreement between the experimental data with the previously presented Redfield-Förster exciton model of Lhca4 strongly supports the equilibration scheme of the bulk excitations with the dynamically localized CT on the stromal side. Thus, a complete picture of the energy transfer pathways leading to the population of the CT final trap within the whole Lhca4 complex is presented. In view of the environmental sensitivity of the CT contribution to the Lhca4 energy landscape, we speculate that one role of the CT states is to regulate the EET from the peripheral antenna to the PSI core
Mixed exciton–charge-transfer states in photosystem II: Stark spectroscopy on site–directed mutants
AbstractWe investigated the electronic structure of the photosystem II reaction center (PSII RC) in relation to the light-induced charge separation process using Stark spectroscopy on a series of site-directed PSII RC mutants from the cyanobacterium Synechocystis sp. PCC 6803. The site-directed mutations modify the protein environment of the cofactors involved in charge separation (PD1, PD2, ChlD1, and PheD1). The results demonstrate that at least two different exciton states are mixed with charge-transfer (CT) states, yielding exciton states with CT character: (PD2δ+PD1δ−ChlD1)∗673nm and (ChlD1δ+PheD1δ−)∗681nm (where the subscript indicates the wavelength of the electronic transition). Moreover, the CT state PD2+PD1− acquires excited-state character due to its mixing with an exciton state, producing (PD2+PD1−)δ∗684nm. We conclude that the states that initiate charge separation are mixed exciton-CT states, and that the degree of mixing between exciton and CT states determines the efficiency of charge separation. In addition, the results reveal that the pigment-protein interactions fine-tune the energy of the exciton and CT states, and hence the mixing between these states. This mixing ultimately controls the selection and efficiency of a specific charge separation pathway, and highlights the capacity of the protein environment to control the functionality of the PSII RC complex
Energy Flow in the Cryptophyte PE545 Antenna Is Directed by Bilin Pigment Conformation
Structure-based calculations are combined with quantitative modeling of spectra and energy transfer dynamics to detemine the energy transfer scheme of the PE545 principal light-harvesting antenna of the cryptomonad Rhodomonas CS24. We use a recently developed quantum-mechanics/molecular mechanics (QM/MM) method that allows us to account for pigment-protein interactions at atomic detail in site energies, transition dipole moments, and electronic couplings. In addition, conformational flexibility of the pigment-protein complex is accounted for through molecular dynamics (MD) simulations. We find that conformational disorder largely smoothes the large energetic differences predicted from the crystal structure between the pseudosymmetric pairs PEB50/61C-PEB50/61D and PEB82C-PEB82D. Moreover, we find that, in contrast to chlorophyll-based photosynthetic complexes, pigment composition and conformation play a major role in defining the energy ladder in the PE545 complex, rather than specific pigment-protein interactions. This is explained by the remarkable conformational flexibility of the eight bilin pigments in PE545, characterized by a quasi-linear arrangement of four pyrrole units. The MD-QM/MM site energies allow us to reproduce the main features of the spectra, and minor adjustments of the energies of the three red-most pigments DBV19A, DBV19B, and PEB82D allow us to model the spectra of PE545 with a similar quality compared to our original model (model E from Novoderezhkin et al. Biophys. J.2010, 99, 344), which was extracted from the spectral and kinetic fit. Moreover, the fit of the transient absorption kinetics is even better in the new structure-based model. The largest difference between our previous and present results is that the MD-QM/MM calculations predict a much smaller gap between the PEB50/61C and PEB50/61D sites, in better accord with chemical intuition. We conclude that the current adjusted MD-QM/MM energies are more reliable in order to explore the spectral properties and energy transfer dynamics in the PE545 complex
Both electronic and vibrational coherences are involved in primary electron transfer in bacterial reaction center
Distinguishing electronic and vibrational coherences helps to clarify the near-unity efficiency of primary electron transfer in reaction centres. Here, the authors report their respective correlation with the electron transfer rate by comparing the 2D electronic spectra of three mutant reaction centres
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