Communication: Kinetic and pairing contributions in the dielectric spectra of electrolyte solutions
- Author(s)
- M. Sega, S. S. Kantorovich, C. Holm, A. Arnold
- Abstract
In the late 1970s, Hubbard and Onsager predicted that adding salt to a polar solution would result in a reduced dielectric permittivity that arises from the unexpected tendency of solvent dipoles to align opposite to the applied field. Here we develop a novel non-equilibrium molecular dynamics simulation approach to determine this decrement accurately. Using a thermodynamic consistent allatom force field we show that for an aqueous solution containing sodium chloride around 4.8 mol/l, this effect accounts for 12% of the total dielectric permittivity. The dielectric decrement can be strikingly different if a less accurate force field for the ions is used. Using the widespread GROMOS parameters, we observe in fact an increment of the dielectric permittivity rather than a decrement, caused by ion pairing and introduced by a too low dispersion force.
- Organisation(s)
- Department of Computational Biological Chemistry, Computational and Soft Matter Physics
- External organisation(s)
- Ural Federal University, Universität Stuttgart
- Journal
- Journal of Chemical Physics
- Volume
- 140
- No. of pages
- 5
- ISSN
- 0021-9606
- DOI
- https://doi.org/10.1063/1.4880237
- Publication date
- 06-2014
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104017 Physical chemistry, 103006 Chemical physics
- Keywords
- ASJC Scopus subject areas
- General Physics and Astronomy, Physical and Theoretical Chemistry
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/1724dc0e-5384-485d-95b6-a503dceee6f9