Mini-grand canonical ensemble: chemical potential in the solvation shell
arXiv:1706.08998 · doi:10.1063/1.4993178
Abstract
Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells' around solutes cannot be described within the macroscopic grand canonical framework using a single chemical potential that represents the solvent `bath'. In this communication, we hypothesize that molecular-sized observation volumes such as solvation shells are best described by coupling the solvation shell with a mixture of particle baths each with its own chemical potential. We confirm our hypotheses by studying the enhanced fluctuations in the occupancy statistics of hard sphere solvent particles around a distinguished hard sphere solute particle. Connections with established theories of solvation are also discussed.
References in corpus (5)
- A maximum entropy thermodynamics of small systems
- Ion-water clusters, bulk medium effects, and ion hydration
- Water coordination structures and the excess free energy of the liquid
- Structure and thermodynamics of a mixture of patchy and spherical colloids: a multi-body association theory with complete reference fluid information
- Thermodynamics of mixtures of patchy and spherical colloids of different sizes: a multi-body association theory with complete reference fluid information