Abstract
The ldquo;activation volume” of reactions in dense media is analyzed in terms of solvent-shift and transport contributions. Transport effects govern the transition from low-pressure gas-phase behaviour into dense-phase diffusion control. Solvent shifts modify energy barrier properties in van der Waals complexes at moderate densities and in solvent cages at high densities. Photoisomerization rates of trans-stilbene are analyzed by the proposed formalism.
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