The spectroscopy of cryogenically cooled, size-selected clusters has proven to be a useful tool with which to determine the molecular-level structures that are responsible for the vibrational response of macroscopic media ranging from water to ionic liquids.  We will describe an emerging set of experimental methods that monitor kinetic processes that occur in composition-selected assemblies as a function of either temperature or internal energy. Specifically, the kinetics that underlie systems in chemical equilibrium can be directly measured using a two-color, IR-IR or uv-uv photochemical hole burning method. This approach is well suited to monitor very slow transformations that occur as rare, spontaneous events.  Several case studies will be presented that reveal the dynamics of spectral diffusion in the vibrational spectrum of water and the water-mediated migration of charge among protomers of functionalized carboxylic acids.

Measuring dynamic equilbria in temperature-controlled, size-selected assemblies: Bringing <i>T</i> and <i>t</i> into the cluster tool kit

ACS Spring Meeting 2021

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Measuring dynamic equilbria in temperature-controlled, size-selected assemblies: Bringing T and t into the cluster tool kit