Effects of ions on hydrogen-bonding water networks in large aqueous nanodrops.

Ensemble infrared photodissociation (IRPD) spectra in the hydrogen stretch region (~2800-3800 cm(-1)) are reported for aqueous nanodrops containing ~250 water molecules and either SO(4)(2-), I(-), Na(+), Ca(2+), or La(3+) at 133 K. Each spectrum has a broad feature in the bonded-OH region (~2800-3500 cm(-1)) and a sharp feature near 3700 cm(-1), corresponding to the free-OH stretch of surface water molecules that accept two hydrogen bonds and donate one hydrogen bond (AAD water molecules). A much weaker band corresponding to AD surface water molecules is observed for all ions except SO(4)(2-). The frequencies of the AAD free-OH stretch red-shift with increasingly positive charge, consistent with a Stark effect as a result of the ion's electric field at the droplet surface, and from which the corresponding frequency for water molecules at the surface of neutral nanodrops of this size is estimated to be 3699.3-3700.1 cm(-1). The intensity of the AAD band increases with increasing positive charge, consistent with a greater population of AAD water molecules for the more positively charged nanodrops. The spectra of M(H(2)O)(~250), M = Na(+) and I(-), are very similar, whereas those for Ca(2+) and SO(4)(2-) have distinct differences. These results indicate that the monovalent ions do not affect the hydrogen-bonding network of the majority of water molecules whereas this network is significantly affected in nanodrops containing the multivalent ions. The ion-induced effect on water structure propagates all the way to the surface of the nanodrops, which is located more than 1 nm from the ion.