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.

Donor-Acceptor Complexes of (5,10,15,20-Tetra(4-methylphenyl)porphyrinato)cobalt(II) with Fullerenes C60: Self-Assembly, Spectral, Electrochemical and Photophysical Properties.

The noncovalent interactions of (5,10,15,20-tetra(4-methylphenyl)porphinato)cobalt(II) (CoTTP) with C60 and 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC60) were studied in toluene using absorption and fluorescence titration methods. The self-assembly in the 2:1 complexes (the triads) (C60)2CoTTP and (PyC60)2CoTTP was established. The bonding constants for (C60)2CoTTP and (PyC60)2CoTTP are defined to be (3.47 ± 0.69) × 109 and (1.47 ± 0.28) × 1010 M-2, respectively. 1H NMR, IR spectroscopy, thermogravimetric analysis and cyclic voltammetry data have provided very good support in favor of efficient complex formation in the ground state between fullerenes and CoTTP. PyC60/C60 fluorescence quenching in the PyC60/C60-CoTTP systems was studied and the fluorescence lifetime with various CoTTP additions was determined. The singlet oxygen quantum yield was determined for PyC60 and the intensity decrease in the 1O2 phosphorescence for C60 and PyC60 with the CoTTP addition leading to the low efficiency of intercombination conversion for the formation of the 3C60* triplet excited state was found. Using femtosecond transient absorption measurements in toluene, the photoinduced electron transfer from the CoTTP in the excited singlet state to fullerene moiety was established. Quantum chemical calculations were used for the determination of molecular structure, stability and the HOMO/LUMO energy levels of the triads as well as to predict the localization of frontier orbitals in the triads.

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.

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.

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.

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.

Comparative Femtosecond Spectroscopy of Primary Photoreactions of Exiguobacterium sibiricum Rhodopsin and Halobacterium salinarum Bacteriorhodopsin.

The primary stages of the Exiguobacterium sibiricum rhodopsin (ESR) photocycle were investigated by femtosecond absorption laser spectroscopy in the spectral range of 400-900 nm with a time resolution of 25 fs. The dynamics of the ESR photoreaction were compared with the reactions of bacteriorhodopsin (bR) in purple membranes (bRPM) and in recombinant form (bRrec). The primary intermediates of the ESR photocycle were similar to intermediates I, J, and K in bacteriorhodopsin photoconversion. The CONTIN program was applied to analyze the characteristic times of the observed processes and to clarify the reaction scheme. A similar photoreaction pattern was observed for all studied retinal proteins, including two consecutive dynamic Stokes shift phases lasting ∼0.05 and ∼0.15 ps. The excited state decays through a femtosecond reactive pathway, leading to retinal isomerization and formation of product J, and a picosecond nonreactive pathway that leads only to the initial state. Retinal photoisomerization in ESR takes 0.69 ps, compared with 0.48 ps in bRPM and 0.74 ps in bRrec. The nonreactive excited state decay takes 5 ps in ESR and ∼3 ps in bR. We discuss the similarity of the primary reactions of ESR and other retinal proteins.

Femtosecond excited state dynamics of stilbene-viologen complexes with a weakly pronounced charge transfer.

The femtosecond dynamics of photoinduced electron transfers in supramolecular donor-acceptor complexes between (E)-bis(18-crown-6)stilbene (D) and tetraperchlorates of 2,7-di(2-ammonioethyl)(2,7-diazapyrenium) (A1), 3,3'-(E)-ethene-1,2-diylbis[1-(3-ammoniopropyl)pyridinium] (A2) and 4,4'-ethane-1,2-diylbis[1-(3-ammoniopropyl)pyridinium] (A3) was studied. The acceptors A2 and A3 are weak electron acceptors whose first reduction potentials are equal to -1.0 and -1.2 V (Ag), respectively, while A1 is a strong acceptor with a reduction potential of -0.42 V. It was shown that the back electron transfer time in CT-states of the complexes D·A2 and D·A3 is 30-40 ps, which is approximately 50 times greater than the analogous time for the charge transfer complexes studied earlier. The complex D·A1 is characterized by ultrafast back electron transfer (770 fs). The relaxation pathway of excited states of D·A1 depends on the wavelength of the excitation light. When excited at 356 nm, the accumulation of a transient locally excited (LE) state with a 250 fs lifetime was observed. But when excited at 425 nm, the formation of the LE-state was not observed.

Generation of ion-radical chlorophyll states in the light-harvesting antenna and the reaction center of cyanobacterial photosystem I.

The energy and charge-transfer processes in photosystem I (PS I) complexes isolated from cyanobacteria Thermosynechococcus elongatus and Synechocystis sp. PCC 6803 were investigated by pump-to-probe femtosecond spectroscopy. The formation of charge-transfer (CT) states in excitonically coupled chlorophyll a complexes (exciplexes) was monitored by measuring the electrochromic shift of ß-carotene in the spectral range 500-510 nm. The excitation of high-energy chlorophyll in light-harvesting antenna of both species was not accompanied by immediate appearance of an electrochromic shift. In PS I from T. elongatus, the excitation of long-wavelength chlorophyll (LWC) caused a pronounced electrochromic effect at 502 nm assigned to the appearance of CT states of chlorophyll exciplexes. The formation of ion-radical pair P700+A1- at 40 ps was limited by energy transfer from LWC to the primary donor P700 and accompanied by carotenoid bleach at 498 nm. In PS I from Synechocystis 6803, the excitation at 720 nm produced an immediate bidentate bleach at 690/704 nm and synchronous carotenoid response at 508 nm. The bidentate bleach was assigned to the formation of primary ion-radical state PB+Chl2B-, where negative charge is localized predominantly at the accessory chlorophyll molecule in the branch B, Chl2B. The following decrease of carotenoid signal at ~ 5 ps was ascribed to electron transfer to the more distant molecule Chl3B. The reduction of phylloquinone in the sites A1A and A1B was accompanied by a synchronous blue-shift of the carotenoid response to 498 nm, pointing to fast redistribution of unpaired electron between two branches in favor of the state PB+A1A-.

Evidence that chlorophyll f functions solely as an antenna pigment in far-red-light photosystem I from Fischerella thermalis PCC 7521.

The Photosystem I (PSI) reaction center in cyanobacteria is comprised of ~96 chlorophyll (Chl) molecules, including six specialized Chl molecules denoted Chl1A/Chl1B (P700), Chl2A/Chl2B, and Chl3A/Chl3B that are arranged in two branches and function in primary charge separation. It has recently been proposed that PSI from Chroococcidiopsis thermalis (Nürnberg et al. (2018) Science 360, 1210-1213) and Fischerella thermalis PCC 7521 (Hastings et al. (2019) Biochim. Biophys. Acta 1860, 452-460) contain Chl f in the positions Chl2A/Chl2B. We tested this proposal by exciting RCs from white-light grown (WL-PSI) and far-red light grown (FRL-PSI) F. thermalis PCC 7521 with femtosecond pulses and analyzing the optical dynamics. If Chl f were in the position Chl2A/Chl2B in FRL-PSI, excitation at 740 nm should have produced the charge-separated state P700+A0- followed by electron transfer to A1 with a τ of ≤25 ps. Instead, it takes ~230 ps for the charge-separated state to develop because the excitation migrates uphill from Chl f in the antenna to the trapping center. Further, we observe a strong electrochromic shift at 685 nm in the final P700+A1- spectrum that can only be explained if Chl a is in the positions Chl2A/Chl2B. Similar arguments rule out the presence of Chl f in the positions Chl3A/Chl3B; hence, Chl f is likely to function solely as an antenna pigment in FRL-PSI. We additionally report the presence of an excitonically coupled homo- or heterodimer of Chl f absorbing around 790 nm that is kinetically independent of the Chl f population that absorbs around 740 nm.

PSI-SMALP, a Detergent-free Cyanobacterial Photosystem I, Reveals Faster Femtosecond Photochemistry.

Cyanobacterial photosystem I (PSI) functions as a light-driven cyt c6-ferredoxin/oxidoreductase located in the thylakoid membrane. In this work, the energy and charge transfer processes in PSI complexes isolated from Thermosynechococcus elongatus via conventional n-dodecyl-ß-D-maltoside solubilization (DM-PSI) and a, to our knowledge, new detergent-free method using styrene-maleic acid copolymers (SMA-PSI) have been investigated by pump-to-probe femtosecond laser spectroscopy. In DM-PSI preparations excited at 740 nm, the excitation remained localized on the long-wavelength chlorophyll forms within 0.1-20 ps and revealed little or no charge separation and oxidation of the special pair, P700. The formation of ion-radical pair P700+A1- occurred with a characteristic time of 36 ps, being kinetically controlled by energy transfer from the long-wavelength chlorophyll to P700. Quite surprisingly, the detergent-free SMA-PSI complexes upon excitation by these long-wave pulses undergo an ultrafast (<100 fs) charge separation in ∼45% of particles. In the remaining complexes (∼55%), the energy transfer to P700 occurred at ∼36 ps, similar to the DM-PSI. Both isolation methods result in a trimeric form of PSI, yet the SMA-PSI complexes display a heterogenous kinetic behavior. The much faster rate of charge separation suggests the existence of an ultrafast pathway for charge separation in the SMA-PSI that may be disrupted during detergent isolation.

Formation of a supramolecular charge-transfer complex. Ultrafast excited state dynamics and quantum-chemical calculations.

The formation of a supramolecular complex of bis(18-crown-6)stilbene (1) and 4,4'-bipyridine with two ammoniopropyl N-substituents (3) and the substitution reaction between 1·3 and alkali and alkaline-earth metal perchlorates have been studied using absorption, steady-state fluorescence, and femtosecond transient absorption spectroscopy. The formation of 1·(Mn+)2 complexes in acetonitrile was demonstrated. The weak long-wavelength charge-transfer absorption band of 1·3 completely vanishes upon complexation with metal cations because of disruption of the pseudocyclic structure. The spectroscopic and luminescence parameters, stability and substitution constants were calculated. The relaxation scheme of the 1·3 singlet state excited by a 25 fs laser pulse was proposed. It includes very fast vibrational relaxation and direct (τCT-d = 0.32 ps) and back (τCT-b = 0.51 ps) electron transfer resulting in complete fluorescence quenching. The quantum-chemistry calculations revealed the species taking part in the ET process and elucidated the mechanism of relaxation of the excited complex.

Monitoring the electric field in CdSe quantum dots under ultrafast interfacial electron transfer via coherent phonon dynamics.

Coherent phonon dynamics in CdSe quantum dots (QD) under an ultrafast electron transfer (ET) reaction of the (1Se-1S3/2) exciton quenched by methyl viologen (MV2+) adsorbed onto the QD surface was studied by ultrafast pump-probe spectroscopy. Frequency and amplitude modulations (FM, AM) of the transient absorption ΔA(ωprobe,t) in the pure CdSe and coupled CdSe/MV2+ QDs were identified in the bleach band dynamics of the red-edge exciton. The fast Fourier transform (FFT) and continuous wavelet transform analysis of the FM and AM oscillations revealed peaks at 0.51-0.58 THz (17-19 cm-1) and 6.06-6.27 THz (202-209 cm-1) attributed to the longitudinal acoustic (LA) and longitudinal optical (LO) phonons, respectively. The electron transfer to MV2+ proceeded non-exponentially with effective time constants of 164 fs (∼30%) and 540 fs (∼70%). The quantum yield of MV˙+ radical formation was 40 ± 5%. It implies a fast route for the electron-hole pair [h+…MV˙+] recombination that can be rationalized in accordance with the adiabatic ET mechanism at the semiconductor surface. In the coupled CdSe/MV2+ QDs, the amplitude of the FM oscillations rose considerably with time despite the natural attenuation of the phonon amplitude due to decoherence processes. A kinetic model explaining the increase of FM oscillations is proposed. The surprising growth of FM oscillations is elucidated by the kinetic model taking into account the relatively slow damping of LO phonon oscillations (∼1.5 ps), the ultrafast ET to MV2+, and the quantum yield of charge separation [h+…MV˙+] (∼40%). The fast formation of the charge-separated pair [h+…MV˙+] suggests the appearance of an electric field F with a strength of ∼3 × 106 V cm-1. The MV2+ reduction substantially increased the magnitude of LA phonon oscillations. Since the ET time is shorter than the period of LA phonon oscillations (∼1.8 ps), the MV2+ reduction substantially increased the magnitude of LA phonon oscillations due to the inverse piezoelectric effect. The CdSe nanocrystals exposed to the electric field F exhibit the quantum-confined Stark and Franz-Keldysh electro-absorption effects. The proposed kinetic model gives consideration to the dynamic Stark shift of the red-edge exciton and to the increased amplitude of LO phonon oscillations in the bleach band dynamics.