Statistical mechanics of sum frequency generation spectroscopy for the liquid-vapor interface of dilute aqueous salt solutions

J Noah-Vanhoucke and JD Smith and PL Geissler, CHEMICAL PHYSICS LETTERS, 470, 21-27 (2009).

DOI: 10.1016/j.cplett.2009.01.028

We demonstrate a theoretical description of vibrational sum frequency generation (SFG) at the boundary of aqueous electrolyte solutions. This approach identifies and exploits a simple relationship between SFG lineshapes and the statistics of molecular orientation and electric field. Our computer simulations indicate that orientational averages governing SFG susceptibility do not manifest ion-specific shifts in local electricfield, but instead, ion-induced polarization of subsurface layers. Counterbalancing effects are obtained for monovalent anions and cations at the same depth. Ions held at different depths induce an imbalanced polarization, suggesting that ion-specific effects can arise from weak, long-ranged influence on solvent organization. (C) 2009 Elsevier B.V. All rights reserved.

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