Abstract
The high-energy tail of the distribution of solute-solvent interaction energies is poorly characterized for condensed systems, but this tail region is of principal interest in determining the excess free energy of the solute. We introduce external fields centered on the solute to modulate the short-range repulsive interaction between the solute and solvent. This regularizes the binding energy distribution and makes it easy to calculate the free energy of the solute with the field. Together with the work done to apply the field in the presence and absence of the solute, we calculate the excess chemical potential of the solute. We present the formal development of this idea and apply it to study liquid water.
Highlights
The high-energy tail of the distribution of solute-solvent interaction energies is poorly characterized for condensed systems, but this tail region is of principal interest in determining the excess free energy of the solute
The excess chemical potential, μexx, of a solute (x) within a general thermodynamic system is that part of the Gibbs free energy that would vanish if the interaction between the solute and solvent were to vanish
The approach leads to a transparent accounting of the hydration thermodynamics and is readily applicable to systems modeled by ab initio potentials or molecularly complex solutes such as proteins
Summary
The high-energy tail of the distribution of solute-solvent interaction energies is poorly characterized for condensed systems, but this tail region is of principal interest in determining the excess free energy of the solute. A generalization of the quasichemical organization [1] of the potential distribution theorem [2], rests on appreciating and exploiting the different energies with which a solute interacts with a solvent at different spatial scales. In this communication we present our results for liquid water modeled by both empirical and ab initio potentials.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
