We define the dielectric constant (susceptibility) that should enter the Maxwell boundary value problem when applied to microscopic dielectric interfaces polarized by external fields. The dielectric constant (susceptibility) of the interface is defined by exact linear-response equations involving correlations of statistically fluctuating interface polarization and the Coulomb interaction energy of external charges with the dielectric. The theory is applied to the interface between water and spherical solutes of altering size studied by molecular dynamics (MD) simulations. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value, and it also depends on the solute size. For TIP3P water used in MD simulations, the interface dielectric constant changes from 9 to 4 when the solute radius is increased from ∼5 to 18 Å.
Details
- Dielectric Constant of Water in the Interface
- Dinpajooh, Mohammadhasan (Author)
- Matyushov, Dmitry (Author)
- College of Liberal Arts and Sciences (Contributor)
- Digital object identifier: 10.1063/1.4955203
- Identifier TypeInternational standard serial numberIdentifier Value1833-3672
- Identifier TypeInternational standard serial numberIdentifier Value1839-3527
- This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in The Journal of Chemical Physics and may be found at http://aip.scitation.org/doi/10.1063/1.4955203.
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Dinpajooh, M., & Matyushov, D. V. (2016). Dielectric constant of water in the interface. The Journal of Chemical Physics, 145(1), 014504. doi:10.1063/1.4955203