水,空气相关离子及溶质的组织:汽/液,液/固界面振动和频光谱测量
he nature of water' s hydrogen-bonding network is a vital influence on the chemistry that occurs at interfaces, but acomplete understanding of interfacial water has proven elusive.Even-order nonlinear optical spectroscopies, such as vibrational sumfrequency generation (VSFG) spectroscopy and heterodyne detectedphase-sensitive sum frequency generation (PS-SFG) spectroscopy,are inherently surface specific. With the advent of advances in thesespectroscopic techniques, researchers can now explore many longstandingquestions about the dynamics and structures present at thevaporwater and watersolid interfaces. Of special interest to theatmospheric chemistry community is the accommodation of ions andsolutes by water' s hydrogen-bonding network. A better understandingof how ions and solutes behave in hydrogen-bonded water has affordeda fresh perspective of aqueous aerosols, because the interactionsinvolved therein drive phenomena such as the hydrolysis of atmosphericchemical species. In this Account, we present work from ourlaboratory focusing on applying VSFG and the recently developed PSSFGtechniques to probe the perturbation ofwater' s hydrogen-bondingnetwork at the vaporwater interface by a variety of ions and solutes.We also present very recent results from our laboratory on the directobservation of the adsorption of ions at the waterCaF2 interface.