Specific counter-cation effect on the molecular orientation of thiocyanate anions at the aqueous solution interface

Abstract

Understanding the interfacial structure of aqueous electrolyte solutions is important and relevant to a wide range of systems, ranging from atmospheric aerosols to electrochemistry, and biological environments. Though significant efforts have been made to unravel the interfacial structure of water molecules, the structure and dynamics of ions at the interface have not yet been fully elucidated. Here, the interfacial structure of the aqueous solution was investigated directly by monitoring the thiocyanate (SCN⁻) anions using surface-specific sum frequency generation (SFG) vibrational spectroscopy. The molecular orientation of the SCN⁻ anions and their adsorption behavior at the air/water interface were systematically determined by quantitative polarization analysis. The transition dipole of the CN stretching of the SCN⁻ anion is oriented around 44° from the surface normal of the NaSCN aqueous solution surface and remained unchanged with the bulk concentration varying from 1 mol kg⁻¹ to 13 mol kg⁻¹. The free energy of adsorption of SCN⁻ anions at the air/water interface was determined to be −1.53 ± 0.04 kcal mol⁻¹. Furthermore, a new SFG peak positioned at 2080 cm⁻¹ in the ppp polarization combination was observed at the air/15.0 mol kg⁻¹ NaSCN aqueous solution interface for the first time. Concentration-dependent SFG analysis and density functional theory (DFT) calculation further revealed that the SCN⁻ anions form an ion clustering structure at the air/water interface. The subtle and specific Na⁺ and K⁺ counter-cation effects on the interfacial structure of the SCN⁻ anions at the aqueous solution interface were also observed, which showed that ion cooperativity plays an important role in affecting the interfacial structure of ions at the air/water interface. The results are expected to yield significant insights into the understanding of the structure of aqueous solution surfaces and the molecular level mechanism of the cationic Hofmeister effect.