Kosmotropic Electrolyte (Na<sub>2</sub>CO<sub>3</sub>, NaF) Perturbs the Air/Water Interface through Anion Hydration Shell without Forming a Well-Defined Electric Double Layer
Subhadip Roy, Jahur A. Mondal
Abstract
The ion-driven electric double layer (EDL) and the structural transformation of interfacial water are implicated in unusual reaction kinetics at the air/water interface. By combining heterodyne-detected vibrational sum frequency generation (HD-VSFG) with differential spectroscopy involving simultaneous curve fitting (DS-SCF) analysis, we retrieve electrolyte (Na2CO3 and NaF)-correlated OH-stretch spectra of water at the air/water interface. Vibrational mapping of the perturbed interfacial water with the hydration shell spectra (obtained by DS-SCF analysis of Raman spectra) of the corresponding anion discloses that the kosmotropic electrolytes do not form well-defined EDL at the air/water interface. Instead, the interfacial water forms a stronger hydrogen-bond with the surface-expelled anions (CO32– and F–) and becomes more inhomogeneous than the pristine air/water interface. Together, the results reveal that the perturbation of interfacial water by the kosmotropic electrolyte is a “local phenomenon” confined within the hydration shell of the surface-expelled anion.