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SKM 2023 – scientific programme

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CPP: Fachverband Chemische Physik und Polymerphysik

CPP 2: Modeling and Simulation of Soft Matter I

CPP 2.9: Talk

Monday, March 27, 2023, 12:00–12:15, MER 02

Coarse-grained modelling of liquid-liquid and liquid-gas interfaces — •Jakob Filser1, Harald Oberhofer2, Christoph Scheurer1, and Karsten Reuter11Fritz-Haber-Institut der MPG, Berlin, Germany — 2Chair for Theoretical Physics VII, University of Bayreuth

Modelling of dielectric interfaces remains a central challenge in computational chemistry. We present a new method to incorporate solvation effects into density-functional theory calculations of organic adsorbates at liquid-liquid and liquid-gas interfaces.

Simulating a large number of solvent molecules explicitly at first-principles level is generally not computationally tractable. We therefore resort to an implicit solvation approach, treating the solvent as a structureless dielectric continuum. Specifically, we advance the multipole-expansion method, in which we model the interface as the boundary of two semi-infinite media with different permittivity. Gauging the limiting behaviour for moving the solute from one bulk medium into the other is straightforward by referencing experimental transfer free energies. Complementary force-field level MD simulations with explicit solvent molecules are used as a reference for the behaviour at the interface. These calculations yield thermal distributions at atomic scale resolution, allowing for a fine assessment of the role of the solvent structure in the adsorption. In our implicit method, we employ a model for the transition of free energy terms, such as the surface tension, between the two media, aimed at reproducing the above mentioned thermal distributions extracted from an atomistic solvent model.

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