Dresden 2017 – wissenschaftliches Programm

Bereiche | Tage | Auswahl | Suche | Aktualisierungen | Downloads | Hilfe

O: Fachverband Oberflächenphysik

O 35: Solid-Liquid Interfaces: Reactions and Electrochemistry - Theory I

O 35.1: Vortrag

Dienstag, 21. März 2017, 12:15–12:30, HSZ 101

Towards a generally applicable parametrization protocol for first-principles implicit solvation approaches based on the Poisson-Boltzmann method — •Stefan Ringe, Harald Oberhofer, and Karsten Reuter — TU Munich, Garching, Germany

Implicit solvation models are a standard means for efficient first-principles descriptions of solvated systems. Poisson-Boltzmann (PB) methods in particular even provide a mean-field account of ionic effects in electrolytes, which are known to crucially impact chemical stability, geometries or dissociation constants. Although PB methods have been extensively applied, generally applicable parametrization procotols are lacking so far. Recently, we have implemented PB solvation functionality into the full-potential density-functional theory package FHI-aims [1]. Here we argue that experimentally measured Setschenow coefficients, which probe the stability change of solutes with varying ionic strength, offer an intriguing route to determine the ionic parameters entering the PB approach. With a slight modification of the original PB model in terms of a Stern or ion exclusion layer, parameterized as a function of the solute’s electron density, we achieve generally good agreement with experimental data for different alkali halide aqueous solutions.
Ringe, S., Oberhofer, H., Hille, C., Matera, S., Reuter, K., J. Chem. Theory Comput., 2016, 12 (8), pp 4052–4066.