DOI: 10.1063/1.453923. Surface potential of the water liquid

Surface potential of the water liquid–vapor interface

10.1063/1.453923

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The surface potential of the water liquid–vapor interface is studied by molecular dynamics using the TIP4P model. The surface potential predicted by this empirical model is −(130±50)mV. This value for the surface potential is of reasonable magnitude but of opposite sign to the expectations derived from laboratory experiments. The electrostatic potential displays a nonmonotonic variation with depth into the liquid. This nonmonotonic variation is explained on the basis of the nondipolar charge distribution of the H2O molecule and the observation that the more probable molecular orientations in the interfacial region place the molecular symmetry axis near the plane of the interface. It is shown that minor changes in the assumed molecular charge distribution can bring the computed surface potential into agreement with experimental expectations without qualitatively altering the nonmonotonic variation of the electrostatic potential through the interfacial region. Computed quantum mechanical descriptions of the electron distribution of the isolated H2O molecule are not compatible with the surface structure predicted by the TIP4P model and the experimental expectation that the surface potential of the water liquid–vapor interface is small, roughly of the order of 10–100 mV. The surface potential is sensitive to details in the large distance wings of the molecular electron distribution. It is hypothesized that the surface environment qualitatively alters the wings of the distribution from the result obtained by a superposition of the isolated molecule electron densities.

Bibliography

Wilson, M. A., Pohorille, A., & Pratt, L. R. (1988). Surface potential of the water liquidâvapor interface. The Journal of Chemical Physics, 88(5), 3281â3285.

Authors 3

Michael A. Wilson (first)
Andrew Pohorille (additional)
Lawrence R. Pratt (additional)

References 20 Referenced 195

10.1080/00319107708084730 / Phys. Chem. Liq. (1977)
10.1146/annurev.pc.36.100185.002245 / Annu. Rev. Phys. Chem. (1985)
10.1063/1.445869 / J. Chem. Phys. (1983)
10.1021/j100303a002 / J. Phys. Chem. (1987)
10.1063/1.1673462 / J. Chem. Phys. (1970)
{'key': '2024021005580905300_r6'}
10.1039/tf9383401093 / Trans. Faraday Soc. (1938)
10.1021/j100706a019 / J. Phys. Chem. (1970)
10.1063/1.433746 / J. Chem. Phys. (1977)
10.1021/j100541a015 / J. Phys. Chem. (1977)
10.1016/0022-0728(82)85102-4 / J. Electroanal. Chem. (1982)
10.1016/0022-0728(85)85055-5 / J. Electroanal. Chem. (1985)
10.1016/S0022-0728(84)80046-7 / J. Electroanal. Chem. (1984)
{'key': '2024021005580905300_r11', 'first-page': '480', 'volume': '10', 'year': '1965', 'journal-title': 'J. Electroanal. Chem.'} / J. Electroanal. Chem. (1965)
10.1039/tf9565201573 / Trans. Faraday Soc. (1956)
10.1039/tf9676301224 / Trans. Faraday Soc. (1967)
{'key': '2024021005580905300_r13'}
{'key': '2024021005580905300_r14'}
{'key': '2024021005580905300_r15'}
10.1063/1.1675388 / J. Chem. Phys. (1971)

Dates

Type	When
Created	23 years ago (July 26, 2002, 9:10 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 2:33 a.m.)
Indexed	1 month, 1 week ago (July 13, 2025, 10:46 p.m.)
Issued	37 years, 5 months ago (March 1, 1988)
Published	37 years, 5 months ago (March 1, 1988)
Published Print	37 years, 5 months ago (March 1, 1988)

Funders 0

None

BibTeX

@article{Wilson_1988, title={Surface potential of the water liquid–vapor interface}, volume={88}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.453923}, DOI={10.1063/1.453923}, number={5}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Wilson, Michael A. and Pohorille, Andrew and Pratt, Lawrence R.}, year={1988}, month=mar, pages={3281–3285} }

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