Diffractive Optics Based Four-Wave, Six-Wave, ... , v-Wave Nonlinear Spectroscopy

A detailed understanding of chemical processes requires information about both structure and dynamics. By definition, a reaction involves nonstationary states and is a dynamic process. Structure describes the atomic positions at global minima in the nuclear potential energy surface. Dynamics are related to the anharmonicities; in this potential that couple different minima and lead to changes in atomic positions (reactions) and correlations. Studies of molecular dynamics can be configured to directly access information on the anharmonic interactions that lead to chemical reactions and are as central to chemistry as structural information. In this regard, nonlinear spectroscopies have distinct advantages over more conventional linear spectroscopies. Because of this potential, nonlinear spectroscopies could eventually attain a comparable level of importance for studying dynamics on the relevant time scales to barrier crossings and reactive processes as NMR has for determining structure. Despite this potential, nonlinear spectroscopy has not attained the same degree of utility as linear spectroscopy largely because nonlinear studies are more technically challenging. For example, unlike the linear spectrometers that exist in almost all chemistry departments, there are no black box four-wave mixing spectrometers. This Account describes recent advances in the application of diffractive optics (DOS) to nonlinear spectroscopy, which reduces the complexity level of this technology to be closer to that of linear spectroscopy. The combination of recent advances in femtosecond laser technology and this single optic approach could bring this form of spectroscopy out of the exclusive realm of specialists and into the general user community. However, the real driving force for this research is the pursuit of higher sensitivity limits, which would enable new forms of nonlinear spectroscopy. This Account chronicles the research that has now extended nonlinear spectroscopy to six-wave processes and to a completely generalized v-wave mixing form to fully control state preparation and coherences. For example, direct observation of global protein motions and energetics has led to the collective mode coupling model to understand structure-function correlations in biological systems. Direct studies of the hydrogen bond network of liquid H(2)O have recently shown that both intramolecular and intermolecular degrees of freedom are strongly coupled so that the primary excitations of water have an excitonic-like character. This fundamentally different view of liquid water has now resolved a 100-year-old problem of homogeneous versus inhomogeneous broadening of the vibrational line shapes. By adding programmable pulse shaping, we can access new information about the many-body interactions directly relevant to chemical reaction dynamics. We can also steer the course of the reaction along multidimensional surfaces to provide information about fluctuations far from the equilibrium, which are most relevant to chemical reactivity.