| Abstract
| - In this paper, the role of entropy and internal energy in determining the free energy surfaces of a model dyemolecule dissolved in nanoconfined solvent is investigated by Monte Carlo simulations. Three solvents (CH3I,CH3CN, and CH3OH) confined in smooth-walled, spherical nanocavities with radii of 10 and 15 Å areconsidered. The results provide insight into the driving forces that determine the differences in position in thenanocavity between the ground and the excited states of the solute, differences that have previously beenshown to be important in time-dependent fluorescence in these systems [J. Chem. Phys.2004, 120, 8125].The results indicate that entropic contributions are central in controlling the shape of the free energy surfacesof the ground and excited-state solute. The effects of solvent molecule shape and charge are explored, andthe possible molecular-level origins of the entropic effects are discussed.
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