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In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of Na 2  + in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of Na 2  + in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For Na 2  + in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. The results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging, and Chemical Identity