Electron Photodetachment from Aqueous Anions. III. Dynamics of Geminate Pairs Derived from Photoexcitation of Mono- vs. Poly- atomic Anions

Photostimulated electron detachment from aqueous inorganic anions is the simplest example of solvent-mediated electron transfer. Here we contrast the behavior of halide anions with that of small polyatomic anions, such as pseudohalide anions (e.g., HS-) and common polyvalent anions (e.g., SO32-). Geminate recombination dynamics of hydrated electrons generated by 200 nm photoexcitation of aqueous anions (I-, Br-, OH-, HS-, CNS-, CO32-, SO32-, and Fe(CN)64-) have been studied. Prompt quantum yields for the formation of solvated, thermalized electrons and quantum yields for free electrons were determined. Pump-probe kinetics for 200 nm photoexcitation were compared with kinetics obtained at lower photoexcitation energy (225 nm or 242 nm) for the same anions, where possible. Free diffusion and mean force potential models of geminate recombination dynamics were used to analyze these kinetics. These analyses suggest that for polyatomic anions (including all polyvalent anions studied) the initial electron distribution has a broad component, even at relatively low photoexcitation energy. There seem to be no well-defined threshold energy below which the broadening of the distribution does not occur, as is the case for halide anions. Direct ionization to the conduction band of water is the most likely photoprocess broadening the electron distribution. Our study suggests that halide anions are in the class of their own; electron photodetachment from polyatomic, especially polyvalent, anions follows a different set of rules.Comment: to be submitted to J. Phys. Chem. A; 28 pages, 5 figs + Supplemen

Frequency-domain "single-shot" (FDSS) ultrafast transient absorption spectroscopy using compressed laser pulses. Part I. Basic treatment

Single-shot ultrafast absorbance spectroscopy based on the frequency encoding of the kinetics is analyzed theoretically and implemented experimentally. The kinetics are sampled in the frequency domain using linearly chirped, amplified 33 fs FWHM pulses derived from a Ti:sapphire laser. A variable length grating pair compressor is used to achieve the time resolution of 500-1000 channels per a 2-to-160 ps window with sensitivity > 5x10-4. In terms of the acquisition time, FDSS has an advantage over the pump-probe spectroscopy in a situation when the "noise" is dominated by amplitude variations of the signal, due to the pump and flow instabilities. The possibilities of FDSS are illustrated with the kinetics obtained in multiphoton ionization of water and aqueous iodide and one-photon excitation of polycrystalline ZnSe and thin-film amorphous Si:H. Unlike other "single-shot" techniques, FDSS can be implemented for fluid samples flowing in a high-speed jet and for thin solid samples that exhibit interference fringes; no a priori knowledge of the excitation profile of the pump across the beam is needed. Another advantage is that due to the interference of quasimonochromatic components of the chirped probe pulse, an oscillation pattern near the origin of the FDSS kinetics emerges. This pattern is unique and can be used to determine the complex dielectric function of the photogenerated species.Comment: 29 pages, 10 figure

Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide

The picosecond dynamics of hydroxyl radicals generated in 200 nm photoinduced dissociation of aqueous hydrogen peroxide have been observed through their transient absorbance at 266 nm. It is shown that these kinetics are nearly exponential, with a decay time of ca. 30 ps. The prompt quantum yield for the decomposition of H2O2 is 0.56, and the fraction of hydroxyl radicals escaping from the solvent cage to the water bulk is 64-68%. These recombination kinetics suggest strong caging of the geminate hydroxyl radicals by water. Phenomenologically, these kinetics may be rationalized in terms of the diffusion of hydroxide radicals out of a shallow potential well (a solvent cage) with an Onsager radius of 0.24 nm.Comment: 14 pages, 1 figur

Investigating the retention of intermediate-mass black holes in star clusters using N-body simulations

Contrary to supermassive and stellar-mass black holes (SBHs), the existence of intermediate-mass black holes (IMBHs) with masses ranging between 10^{2-5} Msun has not yet been confirmed. The main problem in the detection is that the innermost stellar kinematics of globular clusters (GCs) or small galaxies, the possible natural loci to IMBHs, are very difficult to resolve. However, if IMBHs reside in the centre of GCs, a possibility is that they interact dynamically with their environment. A binary formed with the IMBH and a compact object of the GC would naturally lead to a prominent source of gravitational radiation, detectable with future observatories. We use N-body simulations to study the evolution of GCs containing an IMBH and calculate the gravitational radiation emitted from dynamically formed IMBH-SBH binaries and the possibility that the IMBH escapes the GC after an IMBH-SBH merger. We run for the first time direct-summation integrations of GCs with an IMBH including the dynamical evolution of the IMBH with the stellar system and relativistic effects, such as energy loss in gravitational waves (GWs) and periapsis shift, and gravitational recoil. We find in one of our models an intermediate mass-ratio inspiral (IMRI), which leads to a merger with a recoiling velocity higher than the escape velocity of the GC. The GWs emitted fall in the range of frequencies that a LISA-like observatory could detect, like the European eLISA or in mission options considered in the recent preliminary mission study conducted in China. The merger has an impact on the global dynamics of the cluster, as an important heating source is removed when the merged system leaves the GC. The detection of one IMRI would constitute a test of GR, as well as an irrefutable proof of the existence of IMBHs.Comment: Accepted for publication by A&A, minor modification

Ultrafast Pulse Radiolysis Using a Terawatt Laser Wakefield Accelerator

We report the first ultrafast pulse radiolysis transient absorption spectroscopy measurements from the Terawatt Ultrafast High Field Facility (TUHFF) at Argonne National Laboratory. TUHFF houses a 20 TW Ti:sapphire laser system that generates 2.5 nC sub-picosecond pulses of multi-MeV electrons at 10 Hz using laser wakefield acceleration. The system has been specifically optimized for kinetic measurements in a pump-probe fashion. This requires averaging over many shots which necessitates stable, reliable generation of electron pulses. The latter were used to generate excess electrons in pulse radiolysis of liquid water and concentrated solutions of perchloric acid. The hydronium ions in the acidic solutions react with the hydrated electrons resulting in the rapid decay of the transient absorbance at 800 nm on the picosecond time scale. Time resolution of a few picoseconds has been demonstrated. The current time resolution is determined primarily by the physical dimensions of the sample and the detection sensitivity. Subpicosecond time resolution can be achieved by using thinner samples, more sensitive detection techniques and improved electron beam quality.Comment: submitted to J. Appl. Phys. 5 figures, 23 page

Geminate recombination of electrons generated by above-the-gap (12.4 eV) photoionization of liquid water

The picosecond geminate recombination kinetics for hydrated electrons generated by 200 nm two photon absorption (12.4 eV total energy) has been measured in both light and heavy water. The geminate kinetics are observed to be almost identical in both H2O and D2O. Kinetic analysis based upon the independent reaction time approximation indicates that the average separation between the electron and its geminate partners in D2O is 13% narrower than in H2O (2.1 nm vs. 2.4 nm). These observations suggest that, even at this high ionization energy, autoionization of water competes with direct ionization.Comment: 10 pages + 2 figures, submitted to Chem. Phys. Letter

Electrode Strip Deposition for the CMS Barrel Drift Tube System

The full production ideation, design, set up and realization of the Electrode Strip Deposition for the entire construction of the CMS Barrel Drift Tube System are described in detail