Content area
Abstract
Triply Vibrationally Enhanced Four-Wave Mixing (TRIVE FWM) is a coherent multidimensional spectroscopy that provides significant structural and dynamical information about molecules. It utilizes three mid-infrared laser beams to probe coherences between vibrational states. Continued development of TRIVE FWM involves understanding specific features, such as quantum beating and coherence transfer, and extending its application to common types of organic molecules. Frequency-domain quantum beating appears as a spectral line-splitting that oscillates as a function of the time delay between the laser pulses. The observed quantum beating in nickel(0) triphenylphosphine tricarbonyl defined the frequency difference between two unresolved vibrational states. TRIVE FWM experiments investigated coherence transfer, an amplitude-level process in which a coherence evolves to a different coherence without loss of phase information, in nickel(0) bis(triphenylphosphine) dicarbonyl and rhodium(I) dicarbonyl acetylacetonate. TRIVE FWM can isolate coherence transfer processes and resolve the coherence pathways that are responsible for coherence transfer. Finally, TRIVE FWM experiments examined the interactions of ring stretching modes in pyridine, quinoline, and 1,3-dichlorobenzne and C–H bending and stretching modes in octane and dotriacontane. The experiments provide new insights into important interactions between these vibrational modes in aromatic and alkane molecules.
