Surface Prevalence of Perchlorate Anions at the Air/Aqueous Interface.

Air/aqueous interfaces provide a unique environment for many chemical, environmental, and biological processes. To gain insight, molecular-level understanding of the interfacial water organization and ion distributions at these interfaces is required. Here, the air/aqueous interface of NaClO4 salt solutions was investigated by means of conventional and heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. It is found that perchlorate (ClO4(-)) ions exist in the interfacial region and prefer to reside on average above their counterions. This finding is inferred from the average orientation of the OH transition dipole moment of interfacial water molecules governed by the direction of the net electric field arising from the interfacial ion distributions. At the air/aqueous interface of NaClO4 salt solutions, the net dipole moments of hydrogen-bonded water molecules are oriented preferentially toward the vapor phase. Contrary to some other salts (e.g., sulfates), the presence of ClO4(-) may cause a full reversal in the direction of the interfacial electric field at a higher concentration (≥1.7 M). Another interpretation for the positive Im χ((2)) spectra of NaClO4 salt solutions could be an increase in the population of water species contributing positively to the net OH transition dipole moment. Regardless of the mechanism, this effect becomes even more pronounced with increasing salt concentration.