Real-time structural dynamics of the ultrafast solvation process around photo-excited aqueous halides.

This work investigates and describes the structural dynamics taking place following charge-transfer-to-solvent photo-abstraction of electrons from I- and Br- ions in aqueous solution following single- and 2-photon excitation at 202 nm and 400 nm, respectively. A Time-Resolved X-ray Solution Scattering (TR-XSS) approach with direct sensitivity to the structure of the surrounding solvent as the water molecules adopt a new equilibrium configuration following the electron-abstraction process is utilized to investigate the structural dynamics of solvent shell expansion and restructuring in real-time. The structural sensitivity of the scattering data enables a quantitative evaluation of competing models for the interaction between the nascent neutral species and surrounding water molecules. Taking the I0-O distance as the reaction coordinate, we find that the structural reorganization is delayed by 0.1 ps with respect to the photoexcitation and completes on a time scale of 0.5-1 ps. On longer time scales we determine from the evolution of the TR-XSS difference signal that I0: e- recombination takes place on two distinct time scales of ∼20 ps and 100 s of picoseconds. These dynamics are well captured by a simple model of diffusive evolution of the initial photo-abstracted electron population where the charge-transfer-to-solvent process gives rise to a broad distribution of electron ejection distances, a significant fraction of which are in the close vicinity of the nascent halogen atoms and recombine on short time scales.

Classical Spin Liquid or Extended Critical Range in h-YMnO_{3}?

Neutron spectroscopy on the classical triangular-lattice frustrated antiferromagnet h-YMnO_{3} reveals diffuse, gapless magnetic excitations present both far below and above the ordering temperature. The correlation length of the excitations increases as the temperature approaches zero, bearing a strong resemblance to critical scattering. We model the dynamics in the ordered and correlated disordered phase as critical spin correlations in a two-dimensional magnetic state. We propose that our findings may provide a general framework to understand features often attributed to classical spin liquids.