Skip to main content Accessibility help

Role of hydration forces in the properties of electrolyte solutions in the bulk and at interfaces

  • Maria L. Sushko (a1) and Kevin M. Rosso (a1)


We present a theoretical approach for modeling electrolyte solutions at interfaces that reaches into the mesoscale while retaining molecular detail. The total Hamiltonian of the system includes interactions arising from density and charge density (ion correlation) fluctuations, direct Coulomb interactions between ions, and at interfaces the image interactions, ion-solid and ion-water dispersion interactions. The model was validated against its ability to reproduce ion activity in 1:1 and 2:1 electrolyte solutions in the 0-2 M concentration range, its ability to capture the ion-specific effect in 1:1 electrolytes at the air-water interface, and solvent structure in a confined environment between hydrophobic surfaces, revealing the central role of ion hydration interactions in specific ion thermodynamic properties in the bulk solutions and at interfaces. The model is readily extensible to treat electrolyte interactions and forces across charged solid-water interfaces.


Corresponding author


Hide All
1. Ford, I. J., P I Mech Eng C-J Mec, 2004, 218, 883899.
2. Roth, R., Journal of Physics-Condensed Matter, 2010, 22, 063102.
3. Wu, J. Z. and Li, Z. D., Annu. Rev. Phys. Chem., 2007, 58, 85112.
4. Yu, Y. X. and Wu, J. Z., J. Chem. Phys., 2002, 117, 1015610164.
5. Blum, L., Mol. Phys., 1975, 30, 15291535.
6. Hoye, J. S. and Blum, L., Mol. Phys., 1978, 35, 299300.
7. Kjellander, R. and Marcelja, S., J. Chem. Phys., 1985, 82, 21222135.
8. Meng, D., Zheng, B., Lin, G. and Sushko, M. L., Comm. Comp. Phys., 2014, 16, 12981322.
9. CRC handbook of chemistry and physics :, 2014.
10. Tobias, D. J., Stern, A. C., Baer, M. D., Levin, Y. and Mundy, C. J., Annu Rev Phys Chem, 2013, 64, 339359.
11. Horinek, D., Herz, A., Vrbka, L., Sedlmeier, F., Mamatkulov, S. I. and Netz, R. R., Chem. Phys. Lett., 2009, 479, 173183.
12. Stern, A. C., Baer, M. D., Mundy, C. J. and Tobias, D. J., J. Chem. Phys., 2013, 138, 114709.
13. Tuma, L., Jenicek, D. and Jungwirth, P., Chem. Phys. Lett., 2005, 411, 7074.
14. Medasani, B., Ovanesyan, Z., Thomas, D. G., Sushko, M. L. and Marucho, M., J. Chem. Phys., 2014, 140, 204510.
15. Liu, Y. C., Wang, Q. and Lu, L. H., Chem. Phys. Lett., 2003, 381, 210215.


Related content

Powered by UNSILO

Role of hydration forces in the properties of electrolyte solutions in the bulk and at interfaces

  • Maria L. Sushko (a1) and Kevin M. Rosso (a1)


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.