Solvent Control of Chemical Identity Can Change Photodissociation into Photoisomerization.

In solution-phase chemistry, the solvent is often considered to be merely a medium that allows reacting solutes to encounter each other. In this work, however, we show that moderate locally specific solute-solvent interactions can affect not only the nature of the solute but also the types of reactive chemistry. We use quantum simulation methods to explore how solvent participation in solute chemical identity alters reactions involving the breaking of chemical bonds. In particular, we explore the photoexcitation dynamics of Na dissolved in liquid tetrahydrofuran. In the gas phase, excitation of Na directly leads to dissociation, but in solution, photoexcitation leads to an isomerization reaction involving rearrangement of the first-shell solvent molecules; this isomerization must go to completion before the solute can dissociate. Despite the complexity, the solution-phase reaction dynamics can be captured by a two-dimensional energy surface where one dimension involves only the isomerization of the first-shell solvent molecules.