In a liquid solution, intermolecular solute-solvent interactions affect the energies of, and crossings between electronically excited states of photochemically active solute molecules. At ambient temperature, specific intermolecular interactions such as hydrogen bonds fluctuate on ultrafast timescales and will influence the non-adiabatic pathways taken by photoexcited chromophores.  Comparison of the ultrafast photochemical dynamics observed in solution with those for isolated, gas-phase molecules can reveal how such solute-solvent interactions influence the excited-state relaxation pathways and the outcomes of photoinduced reactions.  Our recent studies of the ultrafast photochemical dynamics of various organic chromophores in solvents chosen for their different physical properties will be contrasted with the photodynamics of isolated molecules to unravel the influences of specific solvent-solute interactions.  Examples will be drawn from our experimental and computational investigations of ultrafast non-adiabatic dynamics in aromatic and heterocyclic organic compounds.

Effects of solvent-solute interactions on ultrafast non-adiabatic photochemical pathways

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