Transient x-ray absorption spectroscopy of hydrated halogen atom

Time-resolved x-ray absorption spectroscopy has been used to observe the transient species generated by one-photon detachment of an electron from aqueous bromide. The K-edge spectrum of the short-lived Br-0 atom exhibits a resonant 1s-4p transition that is absent for the Br- precursor. The strong 1s-4p resonance suggests that there is very little charge transfer from the solvent to the open-shell atom, whereas weak oscillations above the absorption edge indicate that the solvent shell around a neutral Br-0 atom is defined primarily by hydrophobic interactions. These conclusions are in agreement with Monte Carlo and quantum chemical simulations of the solvent structure. (C) 2008 American Institute of Physics.