PNNL

Abstract

A liquid microjet was employed to examine the gas/liquid interface of aqueous sodium halide (Na+X-, X=Cl, Br, I) salt solutions. Laser excitation at 193 nm produced and removed cations of the form H+(H2O)n and Na+(H2O)m from liquid jet surfaces containing either NaCl, NaBr or NaI. The protonated water cluster yield varied inversely with increasing salt concentration, while the solvated sodium ion cluster yield varied by anion type. The distribution of H+(H2O)n at low salt concentration is identical to that observed from low-energy electron irradiated amorphous ice and the production of these clusters can be accounted for using a localized ionization/Coulomb expulsion model. Production of Na+(H2O)m is not accounted for by this model but requires ionization of solvation shell waters and a contact ion/Coulomb expulsion mechanism. The reduced yields of Na+(H2O)m from high concentration (10-2 and 10-1 M) NaBr and NaI solutions indicate a propensity for Br- and I- at the solution surfaces and interfaces. This is supported by the observation of multiphoton induced production and desorption of Br+ and I+ from the 10-2 and 10-1 M solution surfaces.