Second-order nonlinear optics can be used to quantitatively determine the orientation of chemical bonds or submoieties of a fairly complicated molecule at an interface, and therefore completely map out its orientation and conformation. As a specific example, we have studied pentyl-cyanoterphenyl molecules at the air-water interface. We have measured the orientation of all three parts of the molecule ͑cyano head group, terphenyl ring, and pentyl chain͒ by optical second-harmonic generation and infrared-visible sum-frequency generation. A quantitatively consistent picture of the molecular configuration has been obtained. The technique can be applied to situations where other methods would fail ͑e.g., the surface of neat liquids or buried interfaces͒.

Liquid interfaces play a fundamental role in science and technology. The development of surface-sensitive probes capable of yielding molecular information about these interfaces is of great importance. This paper gives an overview of our and some others' recent work on vibrational spectroscopy of liquid interfaces by the sum-frequency generation (SFG) technique. This technique, being highly surface specific and applicable to all interfaces accessible by light, has been proven to be a most powerful analytical tool for liquid interfaces. A wide range of systems have been studied including neat liquid surfaces, solid/liquid and liquid/liquid interfaces, surfactants at liquid interfaces, and electrochemical interfaces. In many cases, SFG is shown to be the only technique available that can provide detailed information about a liquid interface at the molecular level.