Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 2, Issue 20, Pages 2515-2520Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz200888t
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Funding
- NSF [CHE-0749807, CHE-1111762]
- DOE [DE-FG02-04ER15495]
- U.S. Department of Energy (DOE) [DE-FG02-04ER15495] Funding Source: U.S. Department of Energy (DOE)
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Phase-sensitive sum frequency generation (PS-SFG) spectroscopy, heterodyne detected, was used to investigate the average direction of the transition dipole moment of interfacial water molecules that is intrinsically contained in the sign of the second-order nonlinear susceptibility, chi((2)). The organization of water at air/aqueous inorganic salts interfaces of CaCl2, NaCl, Na2SO4, (NH4)(2)SO4, and Na2CO3 was inferred. We attribute our findings to the net charge separation arising from the ion distributions at the air/water interface assuming similar ion distribution widths for all systems studied. This is most evident for the aqueous ammonium sulfate solution where the electric field has a greater magnitude relative to the other salt solutions studied. The magnitude of the electric field in the interfacial region decreases in the order (NH4)(2)SO4 > Na2SO4 > Na2CO3 >= CaCl2 > NaCl; the electric field is opposite in direction for the sulfate and carbonate salts relative to the chloride salts.
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