Role of Nonpolar Forces in Aqueous Solvation: Computer Simulation Study of Solvation Dynamics in Water Following Changes in Solute Size, Shape, and Charge

The coupling between solvent fluctuations and the electronic states of solutes is critically important in charge transfer and other chemical reactions. This has piqued enormous interest in solvation dynamicssthe study of how solvent motions relax changes in a solute’s charge distribution. In nearly every computer simulation of solvation dynamics, the system is modeled by an atomic or molecular solute whose charge (or higher multipole moment) is suddenly changed, and the motions of the solvent molecules that relax the new charge distribution are monitored. Almost none of this work, however, accounts for the fact that most reacting solutes also undergo significant changes in size and shape as well as charge distribution. For the excited states of dye molecules typically used as probes in solvation experiments or for the atoms and molecules that change oxidation state in charge transfer reactions, we expect changes in reactant size on the order of 5-20%. In this paper, we use computer simulation to explore the differences between dielectric solvation, due to changes in charge distribution, and mechanical solvation, due to changes in size and shape, for a Lennard-Jones sphere in flexible water. The solvation energy for the size changes expected in typical reactions is on the same order as that for the appearance of a fundamental unit of charge, indicating that dielectric and mechanical solvation dynamics should participate at comparable levels. For dielectric solvation, solvent librations dominate the influence spectrum, but we also find a significant contribution from the water bending motion as well as low-frequency translations. The influence spectrum for mechanical solvation, on the other hand, consists solely of low-frequency intermolecular translational motions, leading to mechanical solvation dynamics that are significantly slower than their dielectric counterparts. The spectrum of couplings for various mechanical perturbations (size, shape, or polarizability) depends somewhat on the magnitude of the change, but all types of mechanical relaxation dynamics appear qualitatively similar. This is due to the steepness of the solutesolvent interaction potential, which dictates that the majority of the solvation energy for mechanical changes comes from the translational motion of the closest one or two solvent molecules. Finally, we explore the solvation dynamics for combined changes in both size and charge and find that the resulting dynamics depend sensitively on the sign and magnitude of both the size and charge changes. For some size/charge combinations, the translational and rotational motions that lead to relaxation work cooperatively, producing rapid solvation. For other combinations, the key translational and rotational solvent motions for relaxation are antagonistic, leading to a situation where mechanical solvation becomes rate limiting: solvent rotational motions are “frustrated” until after translational relaxation has occurred. All the results are compared with previous experimental and theoretical studies of solvation dynamics, and the implications for solvent-driven chemical reactions are discussed.