Reactivity and dynamics at liquid interfaces

Department of Chemistry and Biochemistry, University of California, Santa Cruz, CA 95064, USA 

Many phenomena of interest in science and technology take place at the interface between a liquid and a second phase. Corrosion, the operation of solar cells, and the water splitting reaction are examples of chemical processes that take place at the liquid/solid interface. Electron transfer, ion transfer, and proton transfer reactions at the interface between two immiscible liquids are important for understanding processes such as ion extraction, phase transfer catalysis, drug delivery, and ion channel dynamics in membrane biophysics. The study of reactions at the water liquid/vapor interface is of crucial importance in atmospheric chemistry. Understanding the behavior of solute molecules adsorbed at these interfaces and their reactivity is also of fundamental theoretical interest. The surface region is an inhomogeneous environment where the asymmetry in the intermolecular forces may produce unique behavior. 

Because of its importance, it is not surprising that the study of the neat liquid surface, as well as of solute adsorption, spectroscopy, and reactivity, goes back many years. However, up until the last decade of the twentieth century most of the experimental studies involved the measurement of macroscopic properties such as surface tension and surface potential, and generally speaking, the spectroscopic techniques employed lacked the specificity and 

Reviews in Computational Chemistry, Volume 28, First Edition. Edited by Abby L. Parrill and Kenny B. Lipkowitz. 

In parallel to these experimental approaches, much progress has been made in theoretical studies of liquid surfaces. Advances in the statistical mechanics of inhomogeneous fluids have contributed significantly to our understanding of the molecular structure of liquid/solid, liquid/liquid, and liquid/vapor interfaces. However, the mathematical complexity because of losing the spherical symmetry of the bulk has limited the application to mainly calculating a small number of properties (such as density profile, surface tension, and molecular orientation) of neat inhomogeneous liquids.  

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