Universität Stuttgart
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Item Open Access Manipulating wetting and pore filling by wall transparency(2025) Kondrat, Svyatoslav; Schimmele, Lothar; Giacomello, Alberto; Tasinkevych, Mykola; Dietrich, S.Atomically thin walls become increasingly prevalent in modern technologies. Exhibiting a unique property-transparency to interparticle interactions-such walls influence processes as diverse as capacitive energy storage, electron transfer, and wetting. However, the impact of wall transparency on wetting and capillary phenomena remains poorly understood. Herein, we employ classical density functional theory to explore how van der Waals interactions across thin solid walls affect capillarity and substrate wetting. Our findings demonstrate that a fluid-filled, sidewise-open channel beneath a thin wall can drastically enhance the lyophobicity of the wall (hydrophobicity if fluid is water), up to the point of effectively transforming lyophilic surfaces into lyophobic ones. Conversely, a fluid covering a thin wall can convert capillary condensation to drying and induce unusual capillary phases within the channel. These findings highlight the potential of wall transparency as a tool for manipulating channel filling and wetting behaviors, emphasizing its significance for interfacial phenomena and fluid adsorption in porous materials.Item Open Access Coupling mechanisms of magnetic nanoparticles in polymeric environments(2026) Kreissl, Patrick; Holm, Christian (Prof. Dr.)Item Open Access Percolativity of porous media(2022) Hilfer, Rudolf; Hauskrecht, J.Connectivity and connectedness are nonadditive geometric functionals on the set of pore scale structures. They determine transport of mass, volume or momentum in porous media, because without connectivity there cannot be transport. Percolativity of porous media is introduced here as a geometric descriptor of connectivity, that can be computed from the pore scale and persists to the macroscale through a suitable upscaling limit. It is a measure that combines local percolation probabilities with a probability density of ratios of eigenvalues of the tensor of local percolating directions. Percolativity enters directly into generalized effective medium approximations. Predictions from these generalized effective medium approximations are found to be compatible with apparently anisotropic Archie correlations observed in experiment.Item Open Access Charge regulation in soft matter(2026) Beyer, David; Holm, Christian (Prof. Dr.)Item Open Access On extremal domains and codomains for convolution of distributions and fractional calculus(2022) Kleiner, T.; Hilfer, R.It is proved that the class of c-closed distribution spaces contains extremal domains and codomains to make convolution of distributions a well-defined bilinear mapping. The distribution spaces are systematically endowed with topologies and bornologies that make convolution hypocontinuous whenever defined. Largest modules and smallest algebras for convolution semigroups are constructed along the same lines. The fact that extremal domains and codomains for convolution exist within this class of spaces is fundamentally related to quantale theory. The quantale theoretic residual formed from two c-closed spaces is characterized as the largest c-closed subspace of the corresponding space of convolutors. The theory is applied to obtain maximal distributional domains for fractional integrals and derivatives, for fractional Laplacians, Riesz potentials and for the Hilbert transform. Further, maximal joint domains for families of these operators are obtained such that their composition laws are preserved.Item Open Access Coarse-grained simulations of molecular catalysis in confined spaces(2023) Tischler, Ingo; Holm, Christian (Prof. Dr.)Item Open Access Machine learning-driven investigation of the structure and dynamics of the BMIM-BF4 room temperature ionic liquid(2024) Zills, Fabian; Schäfer, Moritz René; Tovey, Samuel; Kästner, Johannes; Holm, ChristianRoom-temperature ionic liquids are an exciting group of materials with the potential to revolutionize energy storage. Due to their chemical structure and means of interaction, they are challenging to study computationally. Classical descriptions of their inter- and intra-molecular interactions require time intensive parametrization of force-fields which is prone to assumptions. While ab initio molecular dynamics approaches can capture all necessary interactions, they are too slow to achieve the time and length scales required. In this work, we take a step towards addressing these challenges by applying state-of-the-art machine-learned potentials to the simulation of 1-butyl-3-methylimidazolium tetrafluoroborate. We demonstrate a learning-on-the-fly procedure to train machine-learned potentials from single-point density functional theory calculations before performing production molecular dynamics simulations. Obtained structural and dynamical properties are in good agreement with computational and experimental references. Furthermore, our results show that hybrid machine-learned potentials can contribute to an improved prediction accuracy by mitigating the inherent shortsightedness of the models. Given that room-temperature ionic liquids necessitate long simulations to address their slow dynamics, achieving an optimal balance between accuracy and computational cost becomes imperative. To facilitate further investigation of these materials, we have made our IPSuite-based training and simulation workflow publicly accessible, enabling easy replication or adaptation to similar systems.Item Open Access Self- and Fick diffusion coefficients in implicit solvent simulations : influence of local aggregation effects and thermodynamic factors(2025) Tovey, Samuel; Holm, Christian; Smiatek, JensIn this article, we discuss the relationship and transition between self- and Fick diffusion coefficients in continuous implicit solvents across different particle densities. By applying the established expressions for self-diffusion and Fick diffusion coefficients in binary solutions, we analyze how the local environment influences diffusion through thermodynamic factors, which can be readily evaluated within the framework of Kirkwood-Buff (KB) theory. These thermodynamic factors, originally defined as derivatives of thermodynamic activity, vary with changes in local particle densities, particularly in the presence of aggregation effects. Consequently, the transition from self- to Fick diffusion coefficients can be understood as a reflection of variations in these thermodynamic factors. Langevin Dynamics simulations at low number densities show excellent agreement with the analytical expressions derived. Overall, our findings provide deeper insight into how local structural environments shape particle dynamics, clarifying the connection between KB theory and the transition from self- to Fick diffusion coefficients.Item Open Access Hedgehog is relayed through dynamic heparan sulfate interactions to shape its gradient(2023) Gude, Fabian; Froese, Jurij; Manikowski, Dominique; Di Iorio, Daniele; Grad, Jean-Noël; Wegner, Seraphine; Hoffmann, Daniel; Kennedy, Melissa; Richter, Ralf P.; Steffes, Georg; Grobe, KayCellular differentiation is directly determined by concentration gradients of morphogens. As a central model for gradient formation during development, Hedgehog (Hh) morphogens spread away from their source to direct growth and pattern formation in Drosophila wing and eye discs. What is not known is how extracellular Hh spread is achieved and how it translates into precise gradients. Here we show that two separate binding areas located on opposite sides of the Hh molecule can interact directly and simultaneously with two heparan sulfate (HS) chains to temporarily cross-link the chains. Mutated Hh lacking one fully functional binding site still binds HS but shows reduced HS cross-linking. This, in turn, impairs Hhs ability to switch between both chains in vitro and results in striking Hh gradient hypomorphs in vivo. The speed and propensity of direct Hh switching between HS therefore shapes the Hh gradient, revealing a scalable design principle in morphogen-patterned tissues.Item Open Access Water structuring induces nonuniversal hydration repulsion between polar surfaces : quantitative comparison between molecular simulations, theory, and experiments(2024) Schlaich, Alexander; Daldrop, Jan O.; Kowalik, Bartosz; Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.Polar surfaces in water typically repel each other at close separations, even if they are charge-neutral. This so-called hydration repulsion balances the van der Waals attraction and gives rise to a stable nanometric water layer between the polar surfaces. The resulting hydration water layer is crucial for the properties of concentrated suspensions of lipid membranes and hydrophilic particles in biology and technology, but its origin is unclear. It has been suggested that surface-induced molecular water structuring is responsible for the hydration repulsion, but a quantitative proof of this water-structuring hypothesis is missing. To gain an understanding of the mechanism causing hydration repulsion, we perform molecular simulations of different planar polar surfaces in water. Our simulated hydration forces between phospholipid bilayers agree perfectly with experiments, validating the simulation model and methods. For the comparison with theory, it is important to split the simulated total surface interaction force into a direct contribution from surface-surface molecular interactions and an indirect water-mediated contribution. We find the indirect hydration force and the structural water-ordering profiles from the simulations to be in perfect agreement with the predictions from theoretical models that account for the surface-induced water ordering, which strongly supports the water-structuring hypothesis for the hydration force. However, the comparison between the simulations for polar surfaces with different headgroup architectures reveals significantly different decay lengths of the indirect water-mediated hydration-force, which for laterally homogeneous water structuring would imply different bulk-water properties. We conclude that laterally inhomogeneous water ordering, induced by laterally inhomogeneous surface structures, shapes the hydration repulsion between polar surfaces in a decisive manner. Thus, the indirect water-mediated part of the hydration repulsion is caused by surface-induced water structuring but is surface-specific and thus nonuniversal.