New Mixed Vibrational-Electronic Methods in Fully Coherent Multidimensional Spectroscopy: Progress Toward Metal Active Site Characterization

The work presented in this thesis describes new techniques in Coherent Multidimensional Spectroscopy (CMDS). CMDS is an emerging field that is the optical analogue to multidimensional NMR, and its experiments traditionally seek couplings between either vibrational or electronic states. This thesis focuses on a new CMDS pathway that looks for couplings between vibrational and electronic states. The development of new pathways like this will extend the utility of CMDS just as new pulses sequences extended the utility of NMR. This new pathway has many similarities to resonance Raman, but its selectivity and enhancements are different.;The discovery of the resonance Raman effect was a critical advancement for Raman spectroscopy. By using an excitation source resonant with an electronic state coupled to the vibrations of interest, the Raman intensity of those vibrations could be increased by many orders of magnitude. This enhancement allowed resonance Raman to become an important technique in inorganic and bioinorganic spectroscopy, where the metal centers confer unique electronic states to the active site of interest. However, many molecules have enough symmetry for vibrational modes to have very different Raman and infrared activities, leaving some vibrations of interest weak in resonance Raman. The technique presented in this thesis allows electronic enhancement for IR-active modes. It is also a 3-color experiment, resulting in two-dimensional vibrational spectra that are resonantly enhanced by a coupled electronic transition.;This thesis describes the behavior of this "triple sum frequency" technique for three different cases. It also draws comparison to a related CMDS pathway - Doubly Vibrationally Enhanced four-wave mixing. Progress in application of the technique to protein-relevant systems is also discussed.