Graduation Year


Document Type




Degree Granting Department


Major Professor

Brian Space, Ph.D.


Water, Molecular dynamics, Liquid/vapor interface, Nonlinear spectroscopy, SFG


Nonlinear optical processes probe systems in unique manners. The signals obtained from nonlinear spectroscopic experiments are often significantly different than more standard linear techniques, and their intricate nature can make it difficult to interpret the experimental results. Given the complexity of many nonlinear lineshapes, it is to the benefit of both the theoretical and experimental communities to have molecularly detailed computationally amenable theories of nonlinear spectroscopy. Development of such theories, bench marked by careful experimental investigations, have the ability to understand the origins of a given spectroscopic lineshape with atomistic resolution. With this goal in mind, this manuscript details the development of several novel theories of nonlinear surface specific spectroscopies. Spectroscopic responses are described by quantum mechanical quantities. This work shows how well defined classical limits of these expressions can be obtained, and unlike the formal quantum mechanical expressions, the derived expressions comprise a computationally tractable theory. Further, because the developed novel theories have a well defined classical limit, there is a quantum classical correspondence. Thus, semiclassical computational techniques can capture the true physics of the given nonlinear optical process. The semiclassical methodology presented in this manuscript consists of two primary components - classical molecular dynamics and a spectroscopic model. For each theory of nonlinear spectroscopy that is developed, a computational implementation methodology is discussed and/or tested.