Abstract
The surface potential at the water liquid-vapor interface is discussed in relation to experimental determinations of bulk absolute ion hydration free energies. It is shown that, rather than the surface potential itself, the net electrostatic potential at the center of an uncharged solute can aid both in relating differences between tabulations of hydration free energies and in explaining differing classical and quantum surface potential estimates. Quantum mechanical results for the net potential are consistent with conclusions from previous classical simulations, suggesting a contribution from the net potential that can influence ion density profiles for single ions in water droplets.
Original language | English |
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Pages (from-to) | 1-13 |
Number of pages | 13 |
Journal | Chemical Physics Letters |
Volume | 561-562 |
DOIs | |
State | Published - Mar 13 2013 |
Externally published | Yes |
Funding
I would like to thank Lawrence Pratt, Chris Mundy, Marcel Baer, Greg Schenter, Shawn Kathmann, Dilip Asthagiri, David Rogers, Dominik Horinek, Dor Ben-Amotz, and Keven Leung for helpful comments. This research was supported by NSF Grant CHE-1011746 and a generous grant of computer time at the Ohio Supercomputer Center. Following submission of this paper, I received a paper from John Palmeri titled “The vapor–liquid interface potential of (multi) polar fluids and its influence on ion solvation.” [100] That paper draws several conclusions similar to those presented here.