Search results for "Electron Transfer"
showing 10 items of 282 documents
Through space singlet energy transfers in the light harvesting systems and cofacial bisporphyrin dyads
2010
Recent discoveries from our research groups on the photophysics of a few cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several important investigations about the mechanism of energy transfers and energy migration in light-harvesting devices, notably LH II, in the heavily investigated purple photosynthetic bacteria. The key feature is that for face-to-face and slipped dyads with controlled structure using rigid spacers or spacers with limited flexibilities, our fastest rates for singlet energy transfer are in the 10 × 109 s -1 (i.e. 100 ps time scale) for donor-acceptor distances of ~3.5–3.6 Å. The time scale for energy transfers between different…
Comments on the through space singlet energy transfers and energy migration (exciton) in the light harvesting systems
2008
Recent findings on the photophysical investigations of several cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several serious questions about the mechanism of the energy transfers and energy migration in the light harvesting devices, notably LH II, in the heavily studied purple photosynthetic bacteria. The key issue is that for simple cofacial or slipped dyads with controlled geometry using rigid spacers or spacers with limited flexibilities, the fastest possible rates for singlet energy transfer for three examples are in the 10 x 10(9)s(-1) (i.e. just in the 100 ps time scale) for donor-acceptor distances approaching 3.5-3.6 A. The reported time s…
Probing light-induced conformational transitions in bacterial photosynthetic reaction centers embedded in trehalose-water amorphous matrices.
2004
Abstract The coupling between electron transfer and protein dynamics has been studied in photosynthetic reaction centers (RC) from Rhodobacter sphaeroides by embedding the protein into room temperature solid trehalose–water matrices. Electron transfer kinetics from the primary quinone acceptor (Q A − ) to the photoxidized donor (P + ) were measured as a function of the duration of photoexcitation from 20 ns (laser flash) to more than 1 min. Decreasing the water content of the matrix down to ≈5×10 3 water molecules per RC causes a reversible four-times acceleration of P + Q A − recombination after the laser pulse. By comparing the broadly distributed kinetics observed under these conditions …
Ultrafast Electron Transfer in Photosynthesis: Reduced Pheophytin and Quinone Interaction Mediated by Conical Intersections
2007
The mechanism of electron transfer (ET) from reduced pheophytin (Pheo−) to the primary stable photosynthetic acceptor, a quinone (Q) molecule, is addressed by using high‐level ab initio computations and realistic molecular models. The results reveal that the ET process involving the (Pheo−+Q) and (Pheo+Q−) oxidation states can be essentially seen as an ultrafast radiationless transition between the two hypersurfaces taking place via conical intersections (CIs) and it is favoured when the topology of the interacting moieties make possible some overlap between the lowest occupied molecular orbitals (LUMO) of the two systems. Thus, it is anticipated that large scale motions, which are difficul…
Enhanced electron-transfer properties of cofacial porphyrin dimers through pi-pi interactions
2009
pi-pi assisted: Photoinduced electron transfer from cofacial porphyrin dimers to electron acceptors is prominently accelerated, whereas the back electron transfer is decelerated, relative to the corresponding porphyrin monomer (see figure).The radical cation of zinc tetrapentylporphyrin is dimerized with an excess of the neutral counterpart to form the dimer radical cation in which the unpaired electron is delocalized over both porphyrin rings. The dimeric radical cation exhibits an NIR absorption spectrum characteristic of weak pi-bond formation between the porphyrin rings. When cofacial porphyrin dimers, linked by different spacers, are oxidized such pi-bond formation between the porphyri…
Quantum Chemical Simulations of Excited-State Absorption Spectra of Photosynthetic Bacterial Reaction Center and Antenna Complexes
2011
The semiempirical ZINDO/S CIS configuration interaction method has been used to study the ground- and excited-state absorption spectra of wild type and heterodimer M202HL reaction centers from purple bacterium Rhodobacter sphaeroides as well as of peripheral LH2 and LH3 light harvesting complexes from purple bacterium Rhodopseudomonas acidophila. The calculations well reproduce the experimentally observed excited-state absorption spectra between 1000 and 17,000 cm(-1), despite the necessarily limited number of chromophores and protein subunits involved in the calculations. The electron density analysis reveals that the charge transfer between adjacent chromophores dominates the excited-stat…
Can the Double Exchange Cause Antiferromagnetic Spin Alignment?
2020
The effect of the double exchange in a square-planar mixed-valence dn+1&minus
Localization vs. Delocalization in Molecules and Clusters: Electronic and Vibronic Interactions in Mixed Valence Systems
1996
The interplay between electron delocalization and magnetic interactions play a key role in areas as diverse as solid state chemistry (bulk magnetic materials, superconductors,...) [1] and biology (iron-sulfur proteins, manganese-oxo clusters ...) [2]. In molecular inorganic chemistry these two electronic processes have been traditionally studied independently. Thus, the electron dynamics has been extensively investigated in mixedvalence dimers [3] as exemplified by the Creutz-Taube complex [(NH3)5RuII(pyrazine)RuIII(NH3)5]. In this kind of molecular complexes one extra electron is delocalized over two diamagnetic metal sites. Therefore, they constitute model systems for the study of the ele…
Monte Carlo simulation of correlated electrons in disordered systems
1992
Abstract The properties of many-electron states in disordered systems with long-range electron-eletron interaction are investigated by means of a Monte Carlo simulation. Using the Metropolis algorithm, three-dimensional systems up to 512 sites are systematically analysed. The low-lying excitations are investigated in order to distinguish between one-particle and many-particle hopping. In the interesting regime in which disorder and correlation effects are equally important we find that variable-range hopping is insignificant for electron transfer when compared with the contribution from nearest-neighbour one-electron hopping processes as well as variable-number hopping.
Pressure-induced electron transfer in ferrimagnetic Prussian blue analogs
2003
M\"ossbauer and magnetic susceptibility measurements were performed under pressure on three Prussian blue analogs, ${\mathrm{K}}_{0.1}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.7}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ ${\mathrm{K}}_{0.28}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.76}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ and ${\mathrm{Cs}}_{0.7}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.9}\ensuremath{\cdot}16{\mathrm{H}}_{2}\mathrm{O}.$ A pressure-induced electron transfer ${\mathrm{Co}}^{2+}(S=\frac{3}{2})\ensuremath{-}{\mathrm{Fe}}^{3+}(S=\frac{1}{2})\ensuremath{\rightarrow}{\mathrm{Co}}^{3+}(S=0)\ensuremath{-}{\mathrm{Fe}}^{2+}(S=0)…