The broadening and coalescence of spectroscopic features associated with exchanging species is a well-known consequence of the time-energy uncertainty principle.  This is an effect most widely used in NMR spectroscopy, where the timescale of relevant dynamics is on the scale of milliseconds.  For vibrational spectroscopy, the relevant timescale is on the order to picoseconds and we use this to probe inter-molecular dynamics (proton transfer, complex formation) and intra-molecular dynamics (ligand coordination, rotation).  We use this technique to examine how small changes in the local environment function to change the rate of these dynamics.  We also look at how anchoring these fluxional  molecules to inorganic surfaces affects the ultrafast dynamics.  Thus, dynamics vibrational spectroscopy functions as a sensitive probe of environment for chemical species.

Dynamic vibrational spectroscopy of picosecond inter- and intra-molecular dynamics at inorganic surfaces

244th National Meeting (2012)

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