Photoinduced electron transfer and spin dynamics in mixed porphyrin-quinone solutions studied by time-resolved EPR

From time-resolved direct detection cw EPR with pulsed laser excitation, the photoinduced electron transfer and spin dynamics (CIDEP) in mixed zinc-tetraphenylporphyrin (ZnTPP)/benzo-1,4-quinone (BQ) ethanol solutions were determined as functions of temperature and BQ concentration. At lower temperatures the EPR spectra reveal that mixing of the S and T_?1 states in the charge separated radical pair gains in importance relative to the ST₀ mixing. Furthermore, at lower temperatures, the EPR spectra of the spin-correlated radical pairs of ZnTPP⁺ and BQ⁷ could also be observed. From the temperature/viscosity dependence of the electron transfer rates and of the polarization contributions from the triplet and radical pair mechanisms, deviations from a macroscopic diffusion behaviour are inferred at lower temperatures.     

The magnetic field dependence of the electron spin polarization in consecutive spin correlated radical pairs in type I photosynthetic reaction centres

The magnetic field/microwave frequency dependence of the spin polarized EPR spectra of the sequential spin correlated radical pairs P⁺A^? ₁ and P⁺F^? _x in type I photosynthetic reaction centres is investigated. Experimental data are presented for photosystem (PS) I and reaction centres of heliobacteria at × band (9.7 GHz) and K band (24 GHz). In photosystem I at ambient temperatures the lifetime of A ^? ₁ is ~290 ns and both states are observable by transient EPR. In heliobacteria, electron transfer to F_x occurs within ~600 ps and only the state P⁺F^? _x is observed. The experimental data show a net polarization of P⁺ in the state P⁺F^? _x, which displays a clear dependence on the strength of the external field. The net polarization generated in sequential radical pairs is expected to pass through a maximum as a function of the Zeeman energy when the characteristic time of singlet-triplet mixing is comparable with the lifetime of the precursor. In PS I, the precursor lifetime (290ns) is much longer than the characteristic time of singlet-triplet mixing at × band (9 GHz, 3 kG) and K band (24 GHz, 8 kG). As a result, the observable net polarization decreases with the field strength in this region. In contrast, in heliobacteria, the precursor lifetime (600 ps) is much shorter than the characteristic time of singlet-triplet mixing, and the net polarization increases in the same range of Zeeman energies. The polarization patterns in these two systems can be described using the specific limiting cases of a short lived and long lived precursor radical pair and written as a sum of several contributions. The spectra are simulated on this basis using parameters derived entirely from independent experimental data, and good agreement between the experimental polarization patterns is obtained. The calculated polarization patterns are sensitive to spin dynamics on a timescale much shorter than the spectrometer response time, and the expected influence of a 10 ns component in the electron transfer, as observed optically in some PS I, preparations is discussed. No significant influence from such a component is found in the spin polarization patterns of PS I from the cyanobacterium Synechocystis 6803.     

Magnetic field dependence of the spin—Peierls transition

We consider the effect of a magnetic field on the spin—Peierls transition within mean-field theory. Using a mathematical analogy to the regular Peierls transition and existing results, we derive formulas for the magnetic field dependence of the transition temperature and of the distortion periodicity.     

Studies on coherent and incoherent spin dynamics that control the magnetic field effect on photogenerated radical pairs

Since 1970s, magnetic field effects (MFEs) on photogenerated radical pairs have been the centre of focus in the field of spin chemistry. The MFE attributes to quantum mechanical interconversion between the singlet and triplet radical pair states and subsequent spin-selective recombination reactions. In this New View article, the author picks up two hot topics studied during the last two decades, which are (i) so-called low field effect (LFE) and (ii) 2J-resonance MFE on fixed distance donor–acceptor linked molecules. In both of the topics, quantum mechanical explanations are given referring to recent reports, and some novel calculations have been carried out for bridging theoretical and experimental data for long-lived radical pairs. For the first topic, time domain calculations of coherent state mixing have been carried out for elucidation of hyperfine (HF) structure dependence of the LFE. For the second topic, Monte Carlo simulations of the torsional motion of polyaromatic linker unit have been carried out for the demonstration of fast decoherence in such rigid molecules. From these considerations, future possibilities of MFE studies on photo-functional materials and biomolecules have been indicated.     

Femtosecond electron and spin dynamics in Gd(0001) studied by time-resolved photoemission and magneto-optics

Femtosecond electron and spin dynamics of the Gd(0001) surface are investigated by time-resolved photoemission and second harmonic generation. Upon optical excitation the spin polarization of the surface state is reduced by half while its exchange splitting remains nearly unchanged. Electron-magnon interaction is proposed to facilitate electron-spin-flip scattering among spin-mixed surface and bulk states, which provides a mechanism for ultrafast demagnetization.     

Ultrafast structural dynamics studied by kilohertz time-resolved x-ray diffraction

Ultrashort multi-ke V x-ray pulses are generated by electron plasma produced by the irradiation of femtosecond pulses on metals. These sub-picosecond x-ray pulses have extended the field of x-ray spectroscopy into the femtosecond time domain. However, pulse-to-pulse instability and long data acquisition time restrict the application of ultrashort x-ray systems operating at low repetition rates. Here we report on the performance of a femtosecond laser plasma-induced hard x-ray source that operates at 1-k Hz repetition rate, and provides a flux of 2.0 × 1010 photons/s of Cu Kαradiation. Using this system for time-resolved x-ray diffraction experiments, we record in real time, the transient processes and structural changes induced by the interaction of 400-nm femtosecond pulse with the surface of a 200-nm thick Au(111) single crystal.     

Lattice dynamics in two-photon-excited CdS studied by picosecond time-resolved X-ray diffraction

Lattice dynamics and radiative processes in single-crystal cadmium sulfide induced by two-photon excitation with a femtosecond laser are investigated. The development of lattice expansion is directly observed by picosecond time-resolved X-ray diffraction. The obtained lattice dynamics are explained on the basis of a thermally induced impulsive-strain model. The model calculation indicates that two- and more-photon absorption processes occur and that reflectivity rapidly increases under laser irradiation. In photoluminescence spectroscopy, the spectra for TW cm⁻² excitation are shifted to lower energy and show an additional shoulder at 2.35 eV. Furthermore, emission due to Fabry-Perot laser modes with self-formed cavities was observed under 11 TW cm⁻² excitation. The discrepancy between carrier densities deduced from the lattice expansion and the PL spectra indicates that the predominant process at a higher carrier density is not radiative recombination, but Auger recombination followed by lattice heating.     

Surface plasmon dynamics in silver nanoparticles studied by femtosecond time-resolved photoemission

Multiphoton photoelectron spectroscopy reveals the multiple excitation of the surface plasmon in silver nanoparticles on graphite. Resonant excitation of the surface plasmon with 400 nm femtosecond radiation allows one to distinguish between photoemission from the nanoparticles and the substrate. Two different previously unobserved decay channels of the collective excitation have been identified, namely, decay into one or several single-particle excitations.     

The frequency dependence of phonon interactions at Terahertz-frequencies studied by time-resolved phonon spectroscopy

Phonon properties concerning propagation, frequency spectrum and lifetime in the Terahertz range have been investigated. The phonons have been produced by square wave Joule heating of thin constantan films evaporated onto a strongly doped ruby. Cross sections for phonon scattering at the Cr³⁺ impurity ions of the ruby were determined as a function of frequency. The theoretical estimate for mass defect scattering given by Klemens [9] is found to agree reasonably with the experimental results. Lifetime measurements indicate that phonons in ruby preferentially propagate in the transversal mode. Phonon frequency spectra in the constantan films were measured under experimental conditions, where the strength of electron phonon coupling is significant; thus electron-phonon relaxation times could be obtained as a function of frequency.     

Magnetic field dependence of the spin relaxation rate in optically oriented mercury vapour

The magnetic field dependence of the relaxation rate of ¹⁹⁹Hg has been investigated at low fields in the presence of Ne or N₂. It is shown that there is a correlation time, in the interaction of the Hg nuclear spin with the walls, that is equal to the time between wall collisions. The diffusion coefficients of Hg into N₂ and Ne are evaluated, and the possibility of investigating other correlation times is discussed.     

Energy-gap dynamics of superconducting NbN thin films studied by time-resolved terahertz spectroscopy

Using time-domain terahertz spectroscopy we performed direct studies of the photoinduced suppression and recovery of the superconducting gap in a conventional BCS superconductor NbN. Both processes are found to be strongly temperature and excitation density dependent. The analysis of the data with the established phenomenological Rothwarf-Taylor model enabled us to determine the bare quasiparticle recombination rate, the Cooper pair-breaking rate and the electron-phonon coupling constant, λ=1.1±0.1, which is in excellent agreement with theoretical estimates.     

Spin dynamics in CuGeO3 studied by muon spin rotation

We report a muon spin rotation (SR) study of the magnetic properties of the Cu²⁺ quasi-one-dimensional CuGeO₃ system and its lightly-doped derivative Cu_0.97Zn_0.03GeO₃. Susceptibility measurements on CuGeO₃ show a sudden change in the vicinity of 14 K that has been interpreted before as a magnetic transition to a spin-Peierls state. SR shows no evidence of spin freezing below 14 K, implying that the transition is to a magnetic state with no static (random or ordered) electronic moments. A modest slowing down of the electronic spin dynamics is also identified at this temperature. Similarly, no evidence of a transition to a static magnetic state is found for Cu_0.97Zn_0.03GeO₃ whose susceptibility shows hysteretic behaviour between zero-field and field cooled measurements at 4 K, previously ascribed to spinglass-like behaviour. Given the nature of the muon spin as a local magnetic probe, the present results necessitate a re-interpretation of the origin of the susceptibility anomaly observed in the doped system.     

Magnetic microstructures and their dynamics studied by X-ray microscopy

Full-field soft X-ray microscopy in combination with X-ray magnetic circular dichroism as contrast mechanism is a powerful technique to image with elemental specificity magnetic nanostructures and multilayered thin films at high lateral resolution down to 15nm by using Fresnel zone plates as X-ray optical elements. Magnetization reversal phenomena on a microscopic level are studied by recording the images in varying external magnetic fields. Local spin dynamics at a time resolution below 100ps can be addressed by engaging a stroboscopic pump-and-probe scheme taking into account the time pattern of synchrotron storage rings. Characteristic features of magnetic soft X-ray microscopy are reviewed and an outlook into future perspectives with regard to increased lateral and temporal resolution is given.     

Quantum coherence dynamics of spin pairs in many-spin cluster

We consider the dynamics of a quantum coherence of two chosen spins in systems of dipolar coupled nuclear spins s=1/2 in solid. With the purpose to study this coherence we suggest two different methods. One of them uses the partial trace technique and reduced density matrix. The second method is based on the calculation the intensity of multiple quantum coherences using two-spin operator and the density matrix of the whole spin system. Results of calculations of the multiple-quantum dynamics in spin clusters of various dimensionalities are presented. It is shown that the whole density matrix method is more informative than the method based on the reduced density matrix.     

Optical phonon dynamics of GaAs studied with time-resolved terahertz spectroscopy

We investigate the reflection near the reststrahlen band of the optical phonon in bulk GaAs in the time domain, using time-resolved terahertz spectroscopy. We find that the dynamics of the reflection measured for GaAs differs strongly from the reflection dynamics that would be expected for a TO phonon with a frequency-independent dephasing time.     

Low field RYDMR: effects of orthogonal static and oscillating magnetic fields on radical recombination reactions

Reactions involving spin correlated radical pairs as intermediates are known to be sensitive to applied static and/or oscillating magnetic fields. In the reaction yield detected magnetic resonance (RYDMR) technique, an electromagnetic field in resonance with the electron Zeeman splitting produced by a strong static field is used to perturb the singlet ? triplet interconversion of the radical pair and so to affect the yield of geminate recombination. New experiments are described in which weak radiofrequency fields (? 300μT) in the frequency range 1–80 MHz are applied to radical ion pairs derived from pyrene and 1,3-dicyanobenzene, in the presence of a weak (? 3.0 mT) static magnetic field. Such experiments test the viability of RYDMR in low fields, provide insight into the crossover region between the zero-field and high field cases, and may give information on the distribution of radical pair lifetimes.     

Wave packet dynamics in a quasi-one-dimensional metal-halogen complex studied by ultrafast time-resolved spectroscopy

An ultrafast optical response is studied in a quasi-one-dimensional halogen-bridged mixed-valence metal complex [Pt(en)(2)] [Pt(en)2I2] (ClO4)(4) with ultrafast time resolution. Wave packet motions both in the ground and self-trapped exciton (STE) states are observed as oscillatory modulations in the time-resolved reflectivity. The wave packet motion on the STE potential surface begins after about 50 fs with respect to the photoexcitation. This delay is attributed to the lattice relaxation from the free exciton state to the STE state.     

Polaron dynamics in thin polythiophene films studied with time-resolved photoemission

Femtosecond time-resolved two-photon photoemission spectroscopy is employed to study the dynamics of an excited state in a thin regioregular poly(3-hexylthiophene) (RR-P3HT) film deposited on a conducting polymer poly(3,4-ethylene-dioxythiophene): poly-(styrenesulfonate) (PEDT:PSS) electrode following optical excitation at 2.1 eV. We found that the biexponential decay of this excited state has a fast component (2.6 ps) assigned to bound polaron pairs which recombine quickly or separate to be added to the slow component (7.6 ps). The latter is attributed to polarons generated via charge transfer between adjacent polymer chains.     

Low-frequency molecular dynamics studied by spin-lock field cycling imaging

Spin-lock adiabatic field cycling imaging (SLOAFI) relaxometry was shown to be a useful technique for obtaining a fast study of spin-lattice relaxation dispersion in the rotating frame. The aim of the present article is to describe some technical aspects of the experiment in more detail, while showing simple examples that can be compared with laboratory frame relaxation. We also present here a general discussion of the equations for an off-resonance experiment used to analyze low-frequency molecular dynamics.