Photoinduced charge carrier dynamics of Zn-porphyrin-TiO2 electrodes: the key role of charge recombination for solar cell performance

Time resolved absorption spectroscopy has been used to study photoinduced electron injection and charge recombination in Zn-porphyrin sensitized nanostructured TiO(2) electrodes. The electron transfer dynamics is correlated to the performance of dye sensitized solar cells based on the same electrodes. We find that the dye/semiconductor binding can be described with a heterogeneous geometry where the Zn-porphyrin molecules are attached to the TiO(2) surface with a distribution of tilt angles. The binding angle determines the porphyrin-semiconductor electron transfer distance and charge transfer occurs through space, rather than through the bridge connecting the porphyrin to the surface. For short sensitization times (1 h), there is a direct correlation between solar cell efficiency and amplitude of the kinetic component due to long-lived conduction band electrons, once variations in light harvesting (surface coverage) have been taken into account. Long sensitization time (12 h) results in decreased solar cell efficiency because of decreased efficiency of electron injection.     

Viscosity of suspensions in polymeric solutions

Viscosities of suspended particles in polymeric solutions depend upon dissolved polymer concentration, volume fraction of particles and shear rate. In this analysis of viscosity data, relative viscosity was defined as the ratio of suspension viscosity to solution viscosity at the same shear stress rather than shear rate. These relative viscosities reached asymptotic values at high shear stress for all concentrations of dissolved polymer and for all particle loadings. At a given particle loading, the asymptotic values of relative viscosity were nearly independent of the concentration of dissolved polymer. Realtive viscosities were correlated with volume fraction by the one-constant equation of Maron and Pierce.     

Picosecond kinetics of radiationless relaxations of triphenyl methane dyes. Evidence for a rapid excited-state equilibrium between states of differing geometry

The photophysics of several triphenylmethane (TPM) dyes has been studied in n-alcohols and glycerol/water solutions. We have been able to measure the rate and characterize the viscosity dependence of several radiationless decay channels. We propose a kinetic scheme to account for our observations. Important points in this model are, the existence of more than one ground-state species (in some dyes), a rapid excited-state equilibrium between states of differing geometry and solvent-induced spectral shifts.     

Protochlorophyllide a: A Comprehensive Photophysical Picture

The photochemistry of protochlorophyllide a, a precursor in the biosynthesis of chlorophyll and substrate of the light regulated enzyme protochlorophyllide oxidoreductase, is investigated by pump‐probe spectroscopy. Upon excitation into the lowest lying Q‐band the light induced changes are recorded over a wide range of probe wavelengths in the visible and near‐IR region between 500 and 1000 nm. Following excitation, an initial ultrafast 450 fs process is observed related to the motion out of the Franck‐Condon region on the excited state surface; thus directly unraveling previous suggestions based on time‐resolved fluorescence measurements (ChemPhysChem 2006 , 7, 1727–1733). Furthermore, the data reveals a previously concealed photointermediate, whose formation on a nanosecond timescale matches the overall fluorescence decay and is assigned to a triplet state. The implications of this finding with respect to the photochemistry of NADPH:protochlorophyllide oxidoreductase (POR) are discussed.     

On the Similarity of Pulsating and Accelerating Turbulent Pipe Flows

The near-wall region of an unsteady turbulent pipe flow has been investigated experimentally using hot-film anemometry and two-component particle image velocimetry. The imposed unsteadiness has been pulsating, i.e., when a non-zero mean turbulent flow is perturbed by sinusoidal oscillations, and near-uniformly accelerating in which the mean flow ramped monotonically between two turbulent states. Previous studies of accelerating flows have shown that the time evolution between the two turbulent states occurs in three stages. The first stage is associated with a minimal response of the Reynolds shear stress and the ensemble-averaged mean flow evolves essentially akin to a laminar flow undergoing the same change in flow rate. During the second stage, the turbulence responds rapidly to the new flow conditions set by the acceleration and the laminar-like behavior rapidly disappears. During the final stage, the flow adapts to the conditions set by the final Reynolds number. In here, it is shown that the time-development of the ensemble-averaged wall shear stress and turbulence during the accelerating phase of a pulsating flow bears marked similarity to the first two stages of time-development exhibited by a near-uniformly accelerating flow. The stage-like time-development is observed even for a very low forcing frequency; \(\omega ^{+}=\omega \nu /{\overline {u}}_{\tau }^{2}=0.00073\) (or equivalently, \({l}_{s}^{+}=\sqrt {2/\omega ^{+}}=52\)), at an amplitude of pulsation of 0.5. Some previous studies have considered the flow to be quasi-steady at \({l}_{s}^{+}=52\); however, the forcing amplitude has been smaller in those studies. The importance of the forcing amplitude is reinforced by the time-development of the ensemble-averaged turbulence field. For, the near-wall response of the Reynolds stresses showed a dependence on the amplitude of pulsation. Thus, it appears to exist a need to seek alternative similarity parameters, taking the amplitude of pulsation into account, if the response of different flow quantities in a pulsating flow are to be classified correctly.     

Viscosity dependent radiationless relaxation rate of cyanine dyes. A picosecond laser spectroscopy study

The viscosity dependent radiationless relaxation of several cyanine dyes has been studied by picosecond laser spectroscopy. It was found that the relaxation rate is proportional to η^?α. The value of α, however, is not constant for a certain dye molecule, but is strongly dependent on the kind of solvent used. In n-alcohols for instance α is typically about 1. In glycerol/methanol or glycerol/water mixtures on the other hand α ≈ 0.5. A comparison is made with literature data on orientational relaxation lifetimes of some dyes in similar solvents. It is shown that the radiationless relaxation of cyanine dyes and the orientational relaxation of for instance xanthene dyes changes in roughly the same way as the solvent is changed. This is taken as proof of the proposal that a torsional motion of the heterocyclic quinolyl rings is the main course of the viscosity dependent relaxation of the cyanine dyes studied.     

Photochemical isomerization in the absence of a potential barrier

Different time resolved spectroscopic techniques have been used to investigate the photophysics of the isomerization reaction of 1,1′-diethyl-4,4′-cyanin. The molecule is characterized by a very short excited state lifetime, linear viscosity dependence over a wide viscosity range and no or negative temperature dependence of the reaction rate. The wavelength dependence of the ground state recovery experiment reported earlier (?kessonet al 1986,Chem. Phys. Lett. 126 385) has been shown to be the result of dependence mainly on the analyzing light. We believe that this molecule can be a representative of the barrierless reaction type (E₀ < 0) and that the probe wavelength dependence in the GSR experiment is due to the fact that different spectroscopic techniques may probe different physical events in the case of barrierless reactions, and suggest that it is a result of stimulated emission in combination with the resolution of the movement of the population on the excited state surface.     

The excited-state chemistry of protochlorophyllide a: a time-resolved fluorescence study.

The excited-state processes of protochlorophyllide a, the precursor of chlorophyll a in chlorophyll biosynthesis, are studied using picosecond time-resolved fluorescence spectroscopy. Following excitation into the Soret band, two distinct fluorescence components, with emission maxima at 640 and 647 nm, are observed. The 640 nm emitting component appears within the time resolution of the experiment and then decays with a time constant of 27 ps. In contrast, the 647 nm emitting component is built up with a 3.5 ps rise time and undergoes a subsequent decay with a time constant of 3.5 ns. The 3.5 ps rise kinetics are attributed to relaxations in the electronically excited state preceding the nanosecond fluorescence, which is ascribed to emission out of the thermally equilibrated S(1) state. The 27 ps fluorescence, which appears within the experimental response of the streak camera, is suggested to originate from a second minimum on the excited-state potential-energy surface. The population of the secondary excited state is suggested to reflect a very fast motion out of the Franck-Condon region along a reaction coordinate different from the one connecting the Franck-Condon region with the S(1) potential-energy minimum. The 27 ps-component is an emissive intermediate on the reactive excited-state pathway, as its decay yields the intermediate photoproduct, which has been identified previously (J. Phys. Chem. B 2006, 110, 4399-4406). No emission of the photoproduct is observed. The results of the time-resolved fluorescence study allow a detailed spectral characterization of the emission of the excited states in protochlorophyllide a, and the refinement of the kinetic model deduced from ultrafast absorption measurements.     

Photoinduced Ultrafast Dynamics of Ru(dcbpy)(2)(NCS)(2)-Sensitized Nanocrystalline TiO(2) Films: The Influence of Sample Preparation and Experimental Conditions

In most of the previous ultrafast electron injection studies of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films, experimental conditions and sample preparation have been different from study to study and no studies of how the differences affect the observed dynamics have been reported. In the present paper, we have investigated the influence of such modifications. Pump photon density, environment of the sensitized film (solvent and air), and parameters of the film preparation (crystallinity and quality of the film) were varied in a systematic way and the obtained dynamics were compared to that of a well-defined reference sample: Ru(dcbpy)2(NCS)2-TiO2 in acetonitrile. In some cases, the induced changes in the dynamics were uncorrelated to the electron injection process. High pump photon density (not in the linear response region) and exposure of the sensitized film to air altered the picosecond-time-scale kinetics considerably, and the changes were attributed mostly to degradation of the dye. In other cases, changes in the measured kinetics were related to the electron injection processes: reducing the firing temperature of the nanocrystalline film or making the film via electron beam evaporation (EBE) resulted in a decrease of the overall crystallinity of the film, and the electron injection slowed. In the sensitized EBE films, in addition to an increased contribution of triplet excited-state electron injection, a new electron transfer (ET) process with a time constant of 200 fs was observed.