Multiresonant Coherent Multidimensional Vibrational Spectroscopy of Aromatic Systems: Pyridine, a Model System

Multiresonant four wave mixing has been used to measure the coherent multidimensional spectroscopy (CMDS) of representative aromatic ring modes using pyridine as a model system. This work identifies the cross-peaks that appear between several modes and measures their coherent and incoherent dynamics. The work also explores the consequences of using multiresonant CMDS for molecules with transition moments that are typical of most vibrational modes. Typically, CMDS experiments rely on using transitions with exceptionally large transition moments. To observe cross-peaks, the pyridine concentration was raised until absorption effects became very important. These effects interfere with the parametric CMDS coherence pathways, but they do not make important contributions to the nonparametric pathways.