Microscopic mechanisms of confinement-induced slow solvation.
Several studies show that the dynamics of solvent molecules around a solute slows down in a nanoscale confined geometry compared to the bulk condition. Here we perform numerical simulations to investigate the microscopic mechanisms of such slowing down. We show a substantial slowing down of solvation dynamics around a solute in strong solvophilic confinements due to suppression of fluid diffusion in the presence of solvophilic walls, along with restricted solvent dynamics due to geometrical constraints. The solvation in strong solvophobic confinements becomes slower than the same in the bulk as well, but not as significantly as in the solvophilic case. This is due to the competition between restriction in solvent dynamics and faster in-plane solvent diffusion. We place our findings in perspective of various solvation dominated chemical processes in nanoconfined geometry.
Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences , Block JD, Sector III, Salt Lake, Kolkata 700 098, India.
Amit
A
Das
J
J
Chakrabarti