Singly vibrationally enhanced infrared four wave mixing spectroscopy

Abstract

We describe a new nonlinear, nonparametric process that provides a direct measure of vibrational enhancement in four wave mixing. This process has 14 coherent pathways that create the final coherence. In the limit of no pure dephasing and a single vibrational resonance, the 14 pathways combine into a single process that is vibrationally enhanced. The frequency and concentration dependence expected for this process matches that observed in experiments with the methyl- and methylene C-H stretch vibrations in hexane samples. The third-order nonlinear susceptibility for the C-H vibrations was measured by the interferometric method of Levenson and Bloembergen. The vibrational nonlinearity was observed as a difference between the nonresonant electronic contributions and the contribution that depended on resonance with the vibrational absorption transition. The measurements show that the vibrational enhancement is 50 times larger than the nonresonant electronic contribution and it shows that spectroscopic methods based on resonant nuclear nonlinear polarizations are observable above the electronic nonlinear polarization background. © 1998 American Institute of Physics.