Electrochemical Surface Potential Due to Classical Point Charge Models Drives Anion Adsorption to the Air-Water Interface.
We demonstrate that the driving forces for ion adsorption to the air-water interface for point charge models result from both cavitation and a term that is of the form of a negative electrochemical surface potential. We carefully characterize the role of the free energy due to the electrochemical surface potential computed from simple empirical models and its role in ionic adsorption within the context of dielectric continuum theory. Our research suggests that the electrochemical surface potential due to point charge models provides anions with a significant driving force for adsoprtion to the air-water interface. This is contrary to the results of ab initio simulations that indicate that the average electrostatic surface potential should favor the desorption of anions at the air-water interface. The results have profound implications for the studies of ionic distributions in the vicinity of hydrophobic surfaces and proteins.
†Chemical and Materials Science Division, Pacific Northwest National Laboratory, Richland 99352, Washington.
Marcel D
MD
Baer
‡Department of Chemistry, University of California, Irvine, Irvine, California 92697-2025, United States.
Abraham C
AC
Stern
§Instituto de Física, UFRGS Porto Alegre, RS, 91501-970, Brazil.
Yan
Y
Levin
‡Department of Chemistry, University of California, Irvine, Irvine, California 92697-2025, United States.
Douglas J
DJ
Tobias
†Chemical and Materials Science Division, Pacific Northwest National Laboratory, Richland 99352, Washington.
Christopher J
CJ
Mundy
dielectric continuum theory; free-energy; interfaces; ion solvation; statistical mechanics