Axial Coordinated Manganese(III) Porphyrin/Tetraazaporphyrin - 4-(10-phenylanthracen-9-yl)Pyridine Dyads: Self-Assembly, Structure and Spectral Properties in Ground and Excited States.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1 : 1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, ESR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

Femtosecond optical studies of the primary charge separation reactions in far-red photosystem II from Synechococcus sp. PCC 7335.

Primary processes of light energy conversion by Photosystem II (PSII) were studied using femtosecond broadband pump-probe absorption difference spectroscopy. Transient absorption changes of core complexes isolated from the cyanobacterium Synechococcus sp. PCC 7335 grown under far-red light (FRL-PSII) were compared with the canonical Chl a containing spinach PSII core complexes upon excitation into the red edge of the Qy band. Absorption changes of FRL-PSII were monitored at 278 K in the 400-800 nm spectral range on a timescale of 0.1-500 ps upon selective excitation at 740 nm of four chlorophyll (Chl) f molecules in the light harvesting antenna, or of one Chl d molecule at the ChlD1 position in the reaction center (RC) upon pumping at 710 nm. Numerical analysis of absorption changes and assessment of the energy levels of the presumed ion-radical states made it possible to identify PD1+ChlD1- as the predominant primary charge-separated radical pair, the formation of which upon selective excitation of Chl d has an apparent time of ∼1.6 ps. Electron transfer to the secondary acceptor pheophytin PheoD1 has an apparent time of ∼7 ps with a variety of excitation wavelengths. The energy redistribution between Chl a and Chl f in the antenna occurs within 1 ps, whereas the energy migration from Chl f to the RC occurs mostly with lifetimes of 60 and 400 ps. Potentiometric analysis suggests that in canonical PSII, PD1+ChlD1- can be partially formed from the excited (PD1ChlD1)* state.

Inverted region in the reaction of the quinone reduction in the A1-site of photosystem I from cyanobacteria.

Photosystem I from the menB strain of Synechocystis sp. PCC 6803 containing foreign quinones in the A1 sites was used for studying the primary steps of electron transfer by pump-probe femtosecond laser spectroscopy. The free energy gap (- ΔG) of electron transfer between the reduced primary acceptor A0 and the quinones bound in the A1 site varied from 0.12 eV for the low-potential 1,2-diamino-anthraquinone to 0.88 eV for the high-potential 2,3-dichloro-1,4-naphthoquinone, compared to 0.5 eV for the native phylloquinone. It was shown that the kinetics of charge separation between the special pair chlorophyll P700 and the primary acceptor A0 was not affected by quinone substitutions, whereas the rate of A0 → A1 electron transfer was sensitive to the redox-potential of quinones: the decrease of - ΔG by 400 meV compared to the native phylloquinone resulted in a ~ fivefold slowing of the reaction The presence of the asymmetric inverted region in the ΔG dependence of the reaction rate indicates that the electron transfer in photosystem I is controlled by nuclear tunneling and should be treated in terms of quantum electron-phonon interactions. A three-mode implementation of the multiphonon model, which includes modes around 240 cm-1 (large-scale protein vibrations), 930 cm-1 (out-of-plane bending of macrocycles and protein backbone vibrations), and 1600 cm-1 (double bonds vibrations) was applied to rationalize the observed dependence. The modes with a frequency of at least 1600 cm-1 make the predominant contribution to the reorganization energy, while the contribution of the "classical" low-frequency modes is only 4%.

Femtosecond Dynamics of Excited States of Chlorophyll Tetramer in Water-Soluble Chlorophyll-Binding Protein BoWSCP.

The paper reports on the absorption dynamics of chlorophyll a in a symmetric tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP. It was measured by a broadband femtosecond laser pump-probe spectroscopy within the range from 400 to 750 nm and with a time resolution of 20 fs-200 ps. When BoWSCP was excited in the region of the Soret band at a wavelength of 430 nm, nonradiative intramolecular conversion S3→S1 was observed with a characteristic time of 83 ± 9 fs. When the complex was excited in the region of the Qy band at 670 nm, relaxation transition between two excitonic states of the chlorophyll dimer was observed in the range of 105 ± 10 fs. Absorption spectra of the excited singlet states S1 and S3 of chlorophyll a were obtained. The delocalization of the excited state between exciton-coupled Chl molecules in BoWSCP tetramer changed in time and depended on the excitation energy. When BoWSCP is excited in the Soret band region, an ultrafast photochemical reaction is observed. This could result from the reduction of tryptophan in the vicinity of chlorophyll.

Role of pheophytin a in the primary charge separation of photosystem I from Acaryochloris marina: Femtosecond optical studies of excitation energy and electron transfer reactions.

Photosystem I (PSI) of the cyanobacterium Acaryochloris marina is capable of performing an efficient photoelectrochemical conversion of far-red light due to its unique suite of cofactors. Chlorophyll d (Chl-d) has been long known as the major antenna pigment in the PSI from A. marina, while the exact cofactor composition of the reaction centre (RC) was established only recently by cryo-electron microscopy. The RC consists of four Chl-d molecules, and, surprisingly, two molecules of pheophytin a (Pheo-a), which provide a unique opportunity to resolve, spectrally and kinetically, the primary electron transfer reactions. Femtosecond transient absorption spectroscopy was here employed to observe absorption changes in the 400-860 nm spectral window occurring in the 0.1-500 ps timescale upon unselective antenna excitation and selective excitation of the Chl-d special pair P740 in the RC. A numerical decomposition of the absorption changes, including principal component analysis, allowed the identification of P740(+)Chld2(-) as the primary charge separated state and P740(+)Pheoa3(-) as the successive, secondary, radical pair. A remarkable feature of the electron transfer reaction between Chld2 and Pheoa3 is the fast, kinetically unresolved, equilibrium with an estimated ratio of 1:3. The energy level of the stabilised ion-radical state P740(+)Pheoa3(-) was determined to be ~60 meV below that of the RC excited state. In this regard, the energetics and the structural implications of the presence of Pheo-a in the electron transfer chain of PSI from A. marina are discussed, also in comparison with those of the most diffused Chl-a binding RC.

Long-Term Antimicrobial Performance of Textiles Coated with ZnO and TiO2 Nanoparticles in a Tropical Climate.

This paper reports the results of the large-scale field testing of composite materials with antibacterial properties in a tropical climate. The composite materials, based on a cotton fabric with a coating of metal oxide nanoparticles (TiO2 and/or ZnO), were produced using high-power ultrasonic treatment. The antibacterial properties of the materials were studied in laboratory tests on solid and liquid nutrient media using bacteria of different taxonomic groups (Escherichia coli, Chromobacterium violaceum, Pseudomonas chlororaphis). On solid media, the coatings were able to achieve a >50% decrease in the number of bacteria. The field tests were carried out in a tropical climate, at the Climate test station "Hoa Lac" (Hanoi city, Vietnam). The composite materials demonstrated long-term antibacterial activity in the tropical climate: the number of microorganisms remained within the range of 1−3% in comparison with the control sample for the duration of the experiment (3 months). Ten of the microorganisms that most frequently occurred on the surface of the coated textiles were identified. The bacteria were harmless, while the fungi were pathogenic and contributed to fabric deterioration. Tensile strength deterioration was also studied, with the fabrics coated with metal oxides demonstrating a better preservation of their mechanical characteristics over time, (there was a 42% tensile strength decrease for the reference non-coated sample and a 21% decrease for the sample with a ZnO + CTAB coating).

Comparative Absorption Dynamics of the Singlet Excited States of Chlorophylls a and d.

Transient absorption dynamics of chlorophylls a and d dissolved in tetrahydrofuran was measured by the broadband femtosecond laser pump-probe spectroscopy in a spectral range from 400 to 870 nm. The absorption spectra of the excited S1 singlet states of chlorophylls a and d were recorded, and the dynamics of the of the Qy band shift of the stimulated emission (Stokes shift of fluorescence) was determined in a time range from 60 fs to 4 ps. The kinetics of the intramolecular conversion Qx→Qy (electronic transition S2→S1) was measured; the characteristic relaxation time was 54 ± 3 and 45 ± 9 fs for chlorophylls a and d, respectively.

Effects of Surface Chemical Modification by Ethoxysilanes on the Evolution of 3D Structure and Composition of Porous Monoliths Consisting of Alumina Hydroxide Nanofibrils in the Temperature Range 25-1700 °C.

Bulk nanomaterials with an open porosity offer exciting prospects for creating new functional materials for various applications in photonics, IR-THz optics, metamaterials, heterogeneous photocatalysis, monitoring and cleaning toxic impurities in the environment. However, their availability is limited by the complexity of controlling the process of synthesis of bulk 3D nanostructures with desired physicochemical and functional properties. In this paper, we performed a detailed analysis of influence of a silica monolayer chemically deposited on the surface of a monolithic ultraporous nanostructure, consisting of a 3D nanofibril network of aluminum oxyhydroxide, on the evolution of structure and morphology, chemical composition and phase transformations after heat treatment in the temperature range of 20-1700 °C. The experimental results are interpreted in the framework of a physical model taking into account surface and volume mass transport and sintering kinetics of nanofibrils, which made it possible to estimate activation energies of the surface diffusion and sintering processes. It is shown that the presence of a surface silica monolayer on the surface affects the kinetics of aluminum oxyhydroxide dehydration and inhibits diffusion mass transfer and structural phase transformations. As a result, the overall evolution of the 3D nanostructure significantly differs from that of nanomaterials without surface chemical modification.

In memory of Vladimir Anatolievich Shuvalov (1943-2022): an outstanding biophysicist.

We present here a tribute to one of the foremost biophysicists of our time, Vladimir Anatolievich Shuvalov, who made important contributions in bioenergetics, especially on the primary steps of conversion of light energy into charge-separated states in both anoxygenic and oxygenic photosynthesis. For this, he and his research team exploited pico- and femtosecond transient absorption spectroscopy, photodichroism & circular dichroism spectroscopy, light-induced FTIR (Fourier-transform infrared) spectroscopy, and hole-burning spectroscopy. We remember him for his outstanding leadership and for being a wonderful mentor to many scientists in this area. Reminiscences by many [Suleyman Allakhverdiev (Russia); Robert Blankenship (USA); Richard Cogdell (UK); Arvi Freiberg (Estonia); Govindjee Govindjee (USA); Alexander Krasnovsky, jr, (Russia); William Parson (USA); Andrei Razjivin (Russia); Jian- Ren Shen (Japan); Sergei Shuvalov (Russia); Lyudmilla Vasilieva (Russia); and Andrei Yakovlev (Russia)] have included not only his wonderful personal character, but his outstanding scientific research.

Current state of the primary charge separation mechanism in photosystem I of cyanobacteria.

This review analyzes new data on the mechanism of ultrafast reactions of primary charge separation in photosystem I (PS I) of cyanobacteria obtained in the last decade by methods of femtosecond absorption spectroscopy. Cyanobacterial PS I from many species harbours 96 chlorophyll a (Chl a) molecules, including six specialized Chls denoted Chl1A/Chl1B (dimer P700, or PAPB), Chl2A/Chl2B, and Chl3A/Chl3B arranged in two branches, which participate in electron transfer reactions. The current data indicate that the primary charge separation occurs in a symmetric exciplex, where the special pair P700 is electronically coupled to the symmetrically located monomers Chl2A and Chl2B, which can be considered together as a symmetric exciplex Chl2APAPBChl2B with the mixed excited (Chl2APAPBChl2B)* and two charge-transfer states P700 +Chl2A - and P700 +Chl2B -. The redistribution of electrons between the branches in favor of the A-branch occurs after reduction of the Chl2A and Chl2B monomers. The formation of charge-transfer states and the symmetry breaking mechanisms were clarified by measuring the electrochromic Stark shift of ß-carotene and the absorption dynamics of PS I complexes with the genetically altered Chl 2B or Chl 2A monomers. The review gives a brief description of the main methods for analyzing data obtained using femtosecond absorption spectroscopy. The energy levels of excited and charge-transfer intermediates arising in the cyanobacterial PS I are critically analyzed.

Donor-acceptor interactions of gold(III) porphyrins with cobalt(II) phthalocyanine: chemical structure of products, their spectral characterization and DFT study.

In the context of the development of coordination energy-harvesting systems, the axial bonding of cobalt(II) octakis(3,5-di-tert-butylphenoxy)phthalocyanine (1) with gold(III) 2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(pyridin-4-yl)- and (2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(pyridin-3-yl)porphin (2 and 3), the structure, the spectral/electrochemical properties of the resulting donor-acceptor complexes and photoinduced electron transfer in them are studied. The process of the dyad formation passing as self-assembly in the donor-acceptor phthalocyanine-porphyrin systems was explored using UV-Visible, IR, and 1H NMR spectroscopy and mass spectrometry. The geometric and electronic structures of the dyads were identified using density functional theory (DFT) and time-dependent DFT calculations. The electron transfer in the coordination complexes studied was confirmed by recording the radical ion pairs namely 1˙+ : 2˙-/1˙+ : 3˙- and measuring the kinetics of the photoinduction and decay of these states by a femtosecond laser photolysis technique. The effect of the gold(III) porphyrin macrocycle nature in the lifetime of radical ion pairs was shown. The redox potential values for the coordination dyads and the photoelectrochemical parameters defining their perspective in design and understanding of PET systems were observed using the cyclic voltammetry/amperometry methods and the short-circuited electrochemical cell Ti|a dyad film|0.5 M Na2SO4|Pt, respectively.

Femtosecond laser oocyte enucleation as a low-invasive and effective method of recipient cytoplast preparation.

Recipient cytoplast preparation, commonly performed by DNA aspiration with a needle, inevitably leads to the loss of reprogramming factors. As an alternative to the traditional enucleation technique, femtosecond laser enucleation can eliminate DNA effectively without loss of reprogramming factors and without oocyte puncturing. In this work we have performed oocyte enucleation by destructing the metaphase plate using a 795 nm femtosecond laser. The disability of the enucleated oocytes to develop after the parthenogenetic activation, as well as the lack of DNA staining luminescence, strongly confirms the efficiency of the femtosecond laser enucleation. The parthenogenetic development of oocytes after the cytoplasm treatment suggests a low-invasive effect of the laser enucleation technique.

Nitrogen-Doped Carbon Nanodots Produced by Femtosecond Laser Synthesis for Effective Fluorophores.

Understanding the effect of heteroatom doping is crucial for the design of carbon nanodots (CNDs) with enhanced luminescent properties for fluorescence imaging and light-emitting devices. Here, we study the effect and mechanisms of luminescence enhancement through nitrogen doping in nanodots synthesized by the bottom-up route in an intense femtosecond laser field using the comparative analysis of CNDs obtained from benzene and pyridine. We demonstrate that laser irradiation of aromatic compounds produces hybrid nanoparticles consisting of a nanocrystalline core with a shell of surface-bonded aromatic rings. These nanoparticles exhibit excitation-dependent visible photoluminescence typical for CNDs. Incorporation of nitrogen into pyridine-derived CNDs enhances their luminescence characteristics through the formation of small pyridine-based fluorophores peripherally bonded to the nanoparticles. We identify oxidation of surface pyridine rings as a mechanism of formation of several distinct blue- and green-emitting fluorophores in nanodots, containing pyridine moieties. These findings shed additional light on the nature and formation mechanism of effective fluorophores in nitrogen-doped carbon nanodots produced by the bottom-up route.

Aerosol Dry Printing for SERS and Photoluminescence-Active Gold Nanostructures Preparation for Detection of Traces in Dye Mixtures.

We proposed a novel method of nanostructure preparation for observation of surface-enhanced Raman spectroscopy (SERS) and metal-enhanced fluorescence (MEF) based on the deposition of gold nanoparticles (GNPs) above the thin dye film by dry aerosol printing. We detected various enhanced SERS and MEF signals of films of malachite green (MG) and rhodamine B (RhB) mixtures, depending on the surface packing density of Au NPs on the strip, and found the optimum one to achieve the 3.5 × 105 SERS enhancement. It was shown that statistical methods of chemometrics such as projection on latent structures provided the opportunity to distinguish SERS of MG from 100 ppm RhB in a mixture, whereas separation of MEF signals are feasible even for a mixture of MG and 1 ppm RhB due to two-photon excitation.

Ultrafast Quenching of Excitons in the ZnxCd1-xS/ZnS Quantum Dots Doped with Mn2+ through Charge Transfer Intermediates Results in Manganese Luminescence.

For the first time, a specific time-delayed peak was registered in the femtosecond transient absorption (TA) spectra of ZnxCd1-xS/ZnS (x~0.5) alloy quantum dots (QDs) doped with Mn2+, which was interpreted as the electrochromic Stark shift of the band-edge exciton. The time-delayed rise and decay kinetics of the Stark peak in the manganese-doped QDs significantly distinguish it from the kinetics of the Stark peak caused by exciton-exciton interaction in the undoped QDs. The Stark shift in the Mn2+-doped QDs developed at a 1 ps time delay in contrast to the instantaneous appearance of the Stark shift in the undoped QDs. Simultaneously with the development of the Stark peak in the Mn2+-doped QDs, stimulated emission corresponding to 4T1-6A1 Mn2+ transition was detected in the subpicosecond time domain. The time-delayed Stark peak in the Mn2+-doped QDs, associated with the development of an electric field in QDs, indicates the appearance of charge transfer intermediates in the process of exciton quenching by manganese ions, leading to the ultrafast Mn2+ excitation. The usually considered mechanism of the nonradiative energy transfer from an exciton to Mn2+ does not imply the development of an electric field in a QD. Femtosecond TA data were analyzed using a combination of empirical and computational methods. A kinetic scheme of charge transfer processes is proposed to explain the excitation of Mn2+. The kinetic scheme includes the reduction of Mn2+ by a 1Se electron and the subsequent oxidation of Mn1+ with a hole, leading to the formation of an excited state of manganese.

Intramolecular photo-driven charge transfer in a series of pyridyl substituted phenyloxazoles. Structural relaxation in meta-substituted ethylpyridinium derivative of phenyloxazole.

A series of pyridyl (pyridinium) substituted benzoxazoles were studied by steady state absorption, fluorescence spectroscopy, time-resolved fluorescence spectroscopy, fs pulse absorption and polarization spectroscopy, and quantum-chemical calculations. The spectral and kinetic parameters of the fluorophores in MeCN and EtOAc were obtained experimentally and were calculated by means of DFT and TDDFT methods. A scheme including four transient excited states was proposed for the interpretation of differential absorption kinetics of the charged fluorophores. Expressions describing the actual kinetics graphs, the decay associated spectra, and the species-associated spectra were derived. The charge shift step was found to be dependent on average solvation times. A charge shift followed by the formation of the twisted conformer was found for the excited 1-ethyl-3-(5-phenyloxazol-2-yl)pyridinium 4-methyl-1-benzenesulfonate in MeCN and EtOAc. Conformational analysis confirms a large amplitude motion of the meta-substituted ethylpyridinium group as an additional structural relaxation path producing an abnormally large fluorescence Stokes shift.

Symmetry breaking in photosystem I: ultrafast optical studies of variants near the accessory chlorophylls in the A- and B-branches of electron transfer cofactors.

Femtosecond absorption spectroscopy of Photosystem I (PS I) complexes from the cyanobacterium Synechocystis sp. PCC 6803 was carried out on three pairs of complementary amino acid substitutions located near the second pair of chlorophyll molecules Chl2A and Chl2B (also termed A-1A and A-1B). The absorption dynamics at delays of 0.1-500 ps were analyzed by decomposition into discrete decay-associated spectra and continuously distributed exponential components. The multi-exponential deconvolution of the absorption changes revealed that the electron transfer reactions in the PsaA-N600M, PsaA-N600H, and PsaA-N600L variants near the B-branch of cofactors are similar to those of the wild type, while the PsaB-N582M, PsaB-N582H, and PsaB-N582L variants near the A-branch of cofactors cause significant alterations of the photochemical processes, making them heterogeneous and poorly described by a discrete exponential kinetic model. A redistribution of the unpaired electron between the second and the third monomers Chl2A/Chl2B and Chl3A/Chl3B was identified in the time range of 9-20 ps, and the subsequent reduction of A1 was identified in the time range of 24-70 ps. In the PsaA-N600L and PsaB-N582H/L variants, the reduction of A1 occurred with a decreased quantum yield of charge separation. The decreased quantum yield correlates with a slowing of the phylloquinone A0 → A1 reduction, but not with the initial transient spectra measured at the shortest time delay. The results support a branch competition model, where the electron is sheared between Chl2A-Chl3A and Chl2B-Chl3B cofactors before its transfer to phylloquinone in either A1A or A1B sites.

Role of hydrogen bond alternation and charge transfer states in photoactivation of the Orange Carotenoid Protein.

Here, we propose a possible photoactivation mechanism of a 35-kDa blue light-triggered photoreceptor, the Orange Carotenoid Protein (OCP), suggesting that the reaction involves the transient formation of a protonated ketocarotenoid (oxocarbenium cation) state. Taking advantage of engineering an OCP variant carrying the Y201W mutation, which shows superior spectroscopic and structural properties, it is shown that the presence of Trp201 augments the impact of one critical H-bond between the ketocarotenoid and the protein. This confers an unprecedented homogeneity of the dark-adapted OCP state and substantially increases the yield of the excited photoproduct S*, which is important for the productive photocycle to proceed. A 1.37 Å crystal structure of OCP Y201W combined with femtosecond time-resolved absorption spectroscopy, kinetic analysis, and deconvolution of the spectral intermediates, as well as extensive quantum chemical calculations incorporating the effect of the local electric field, highlighted the role of charge-transfer states during OCP photoconversion.

Unprecedented Coordination-Induced Bright Red Emission from Group 12 Metal-Bound Triarylazoimidazoles.

Arylazoimidazoles are important dyes which were intensively studied in the past. In contrast, triarylazoimidazoles (derivatives which carry aryl substituents at the imidazole core) received almost no attention in the scientific literature. Here, we report a new family of simple and easily accessible triarylazoimidazole-group 12 metal complexes, which feature highly efficient photo-luminescence emission (Φ up to 0.44). Novel compounds exhibit bright red emission in solution, which could be excited with a visible light.

Primary charge separation within the structurally symmetric tetrameric Chl2APAPBChl2B chlorophyll exciplex in photosystem I.

In Photosystem I (PS I), the role of the accessory chlorophyll (Chl) molecules, Chl2A and Chl2B (also termed A-1A and A-1B), which are directly adjacent to the special pair P700 and fork into the A- and B-branches of electron carriers, is incompletely understood. In this work, the Chl2A and Chl2B transient absorption ΔA0(λ) at a time delay of 100 fs was identified by ultrafast pump-probe spectroscopy in three pairs of PS I complexes from Synechocystis sp. PCC 6803 with residues PsaA-N600 or PsaB-N582 (which ligate Chl2B or Chl2A through a H2O molecule) substituted by Met, His, and Leu. The ΔA0(λ) spectra were quantified using principal component analysis, the main component of which was interpreted as a mutation-induced shift of the equilibrium between the excited state of primary donor P700⁎ and the primary charge-separated state P700+Chl2-. This equilibrium is shifted to the charge-separated state in wild-type PS I and to the excited P700 in the PS I complexes with the substituted ligands to the Chl2A and Chl2B monomers. The results can be rationalized within the framework of an adiabatic model in which the P700 is electronically coupled with the symmetrically arranged monomers Chl2A and Chl2B; such a structure can be considered a symmetric tetrameric exciplex Chl2APAPBChl2B, in which the excited state (Chl2APAPBChl2B)* is mixed with two charge-transfer states P700+Chl2A- and P700+Chl2B-. The electron redistribution between the two branches in favor of the A-branch apparently takes place in the picosecond time scale after reduction of the Chl2A and Chl2B monomers.