Theoretical Modeling of Interface Specific Vibrational Spectroscopy:Methods and Applications to Aqueous Interfaces

摘要

Liquid water interfaces are ubiquitous and important in chemistry and the environment.Thus,with the advent of interface specific nonlinear optical spectroscopies,such interfaces have been intensely studied-both theoretically and experimentally.Sum frequency generation(SFG)Spectroscopy is a powerful experimental method for probing the structure and dynamics of interfaces.SFG is a second-order polarization experiment,and the more common electronically nonresonant experiment is the main focus of this review(although the theory of other second-order processes is discussed).SFG Spectroscopy is dipole forbidden in centrosymmetric media-such as liquids.Interfaces serve to break the isotropic symmetry and produce a dipolar second-order signal that is sensitive only to the interface in most cases.