Abstract
▪ Abstract Significant advances toward understanding the structure of aqueous surfaces on a molecular level have been made in recent years. This review focuses on the recent contributions of surface vibrational sum frequency spectroscopy (VSFS) to this field of study. An overview of recent VSFS studies of the molecular structure and orientation of molecules at the vapor-water interface and the interface between water and an immiscible organic liquid is presented, with particular emphasis on studies that compare the molecular properties and adsorbate behavior at these two different but related interfaces. This discussion is preceded by a general introduction to VSFS studies at aqueous surfaces and a description of the fundamental principles underlying the technique.