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

Nematic crossover in BaFe2_2As2_2 under uniaxial stress

Raman scattering can detect spontaneous point-group symmetry breaking without resorting to single-domain samples. Here we use this technique to study $\mathrm{BaFe_2As_2}$, the parent compound of the "122" Fe-based superconductors. We show that an applied compression along the Fe-Fe direction, which is commonly used to produce untwinned orthorhombic samples, changes the structural phase transition at temperature $T_{\mathrm{s}}$ into a crossover that spans a considerable temperature range above $T_{\mathrm{s}}$. Even in crystals that are not subject to any applied force, a distribution of substantial residual stress remains, which may explain phenomena that are seemingly indicative of symmetry breaking above $T_{\mathrm{s}}$. Our results are consistent with an onset of spontaneous nematicity only below $T_{\mathrm{s}}$.Comment: 4 pages, 4 figure

H1H^1-analysis of H3N3-2\textbf{σ_\sigma}-based difference method for fractional hyperbolic equations

A novel H3N3-2$_\sigma$ interpolation approximation for the Caputo fractional derivative of order $\alpha\in(1,2)$ is derived in this paper, which improves the popular L2C formula with (3-$\alpha$)-order accuracy. By an interpolation technique, the second-order accuracy of the truncation error is skillfully estimated. Based on this formula, a finite difference scheme with second-order accuracy both in time and in space is constructed for the initial-boundary value problem of the time fractional hyperbolic equation. It is well known that the coefficients' properties of discrete fractional derivatives are fundamental to the numerical stability of time fractional differential models. We prove the related properties of the coefficients of the H3N3-2$_\sigma$ approximate formula. With these properties, the numerical stability and convergence of the difference scheme are derived immediately by the energy method in the sense of $H^1$-norm. Considering the weak regularity of the solution to the problem at the starting time, a finite difference scheme on the graded meshes based on H3N3-2$_\sigma$ formula is also presented. The numerical simulations are performed to show the effectiveness of the derived finite difference schemes, in which the fast algorithms are employed to speed up the numerical computation