Multilevel vibrational coherence transfer and wavepacket dynamics probed with multidimensional IR spectroscopy.

Multidimensional infrared (MDIR) spectroscopy of a strongly coupled multilevel vibrational system Mn(2)(CO)(10) (dimanganese decacarbonyl) in cyclohexane solution reveals fully resolved excited vibrational state coherences that exhibit slow 0.25-0.50 ps(-1) decay constants. Detailed analysis of the waiting-time dependence of certain cross-peak amplitudes shows modulation at multiple frequencies, providing a direct signature of excited vibrational coherences resulting from coherence transfer. A new signature of coherence transfer is observed as temporally modulated cross-peak amplitudes with more than one modulation frequency. The relative importance of different coherence transfer paths is considered in the context of the orientational response of a system which includes two vibrational modes with parallel dipole moments. Since MDIR spectroscopy enables spectral isolation of individual excited vibrational coherences (i.e., coherences between fundamental excitations), these experiments report directly on the frequency-frequency correlation functions of the excited states relative to each other as well as relative to the ground state. These results highlight the rich information contained in fully exploring three-dimensional third-order spectroscopy, particularly regarding chemically relevant slower dynamics and the importance of intramolecular interactions leading to dephasing by optically dark or low-frequency modes of the molecule.