08 Fakultät Mathematik und Physik
Permanent URI for this collectionhttps://elib.uni-stuttgart.de/handle/11682/9
Browse
12 results
Search Results
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 PDADMAC/PSS oligoelectrolyte multilayers : internal structure and hydration properties at early growth stages from atomistic simulations(2020) Sánchez, Pedro A.; Vögele, Martin; Smiatek, Jens; Qiao, Baofu; Sega, Marcello; Holm, ChristianWe analyze the internal structure and hydration properties of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) oligoelectrolyte multilayers at early stages of their layer-by-layer growth process. Our study is based on large-scale molecular dynamics simulations with atomistic resolution that we presented recently [Sánchez et al., Soft Matter 2019, 15, 9437], in which we produced the first four deposition cycles of a multilayer obtained by alternate exposure of a flat silica substrate to aqueous electrolyte solutions of such polymers at 0.1M of NaCl. In contrast to any previous work, here we perform a local structural analysis that allows us to determine the dependence of the multilayer properties on the distance to the substrate. We prove that the large accumulation of water and ions next to the substrate observed in previous overall measurements actually decreases the degree of intrinsic charge compensation, but this remains as the main mechanism within the interface region. We show that the range of influence of the substrate reaches approximately 3 nm, whereas the structure of the outer region is rather independent from the position. This detailed characterization is essential for the development of accurate mesoscale models able to reach length and time scales of technological interest.Item Open Access Permeability estimation of regular porous structures : a benchmark for comparison of methods(2021) Wagner, Arndt; Eggenweiler, Elissa; Weinhardt, Felix; Trivedi, Zubin; Krach, David; Lohrmann, Christoph; Jain, Kartik; Karadimitriou, Nikolaos; Bringedal, Carina; Voland, Paul; Holm, Christian; Class, Holger; Steeb, Holger; Rybak, IrynaThe intrinsic permeability is a crucial parameter to characterise and quantify fluid flow through porous media. However, this parameter is typically uncertain, even if the geometry of the pore structure is available. In this paper, we perform a comparative study of experimental, semi-analytical and numerical methods to calculate the permeability of a regular porous structure. In particular, we use the Kozeny-Carman relation, different homogenisation approaches (3D, 2D, very thin porous media and pseudo 2D/3D), pore-scale simulations (lattice Boltzmann method, Smoothed Particle Hydrodynamics and finite-element method) and pore-scale experiments (microfluidics). A conceptual design of a periodic porous structure with regularly positioned solid cylinders is set up as a benchmark problem and treated with all considered methods. The results are discussed with regard to the individual strengths and limitations of the used methods. The applicable homogenisation approaches as well as all considered pore-scale models prove their ability to predict the permeability of the benchmark problem. The underestimation obtained by the microfluidic experiments is analysed in detail using the lattice Boltzmann method, which makes it possible to quantify the influence of experimental setup restrictions.Item Open Access Hybrid molecules consisting of lysine dendrons with several hydrophobic tails : a SCF study of self-assembling(2023) Shavykin, Oleg V.; Mikhtaniuk, Sofia E.; Fatullaev, Emil I.; Neelov, Igor M.; Leermakers, Frans A. M.; Brito, Mariano E.; Holm, Christian; Borisov, Oleg V.; Darinskii, Anatoly A.In this article, we used the numerical self-consistent field method of Scheutjens-Fleer to study the micellization of hybrid molecules consisting of one polylysine dendron with charged end groups and several linear hydrophobic tails attached to its root. The main attention was paid to spherical micelles and the determination of the range of parameters at which they can appear. A relationship has been established between the size and internal structure of the resulting spherical micelles and the length and number of hydrophobic tails, as well as the number of dendron generations. It is shown that the splitting of the same number of hydrophobic monomers from one long tail into several short tails leads to a decrease in the aggregation number and, accordingly, the number of terminal charges in micelles. At the same time, it was shown that the surface area per dendron does not depend on the number of hydrophobic monomers or tails in the hybrid molecule. The relationship between the structure of hybrid molecules and the electrostatic properties of the resulting micelles has also been studied. It is found that the charge distribution in the corona depends on the number of dendron generations G in the hybrid molecule. For a small number of generations (up to G=3), a standard double electric layer is observed. For a larger number of generations (G=4), the charges of dendrons in the corona are divided into two populations: in the first population, the charges are in the spherical layer near the boundary between the micelle core and shell, and in the second population, the charges are near the periphery of the spherical shell. As a result, a part of the counterions is localized in the wide region between them. These results are of potential interest for the use of spherical dendromicelles as nanocontainers for drug delivery.Item Open Access The presence of a wall enhances the probability for ring‐closing metathesis : insights from classical polymer theory and atomistic simulations(2020) Tischler, Ingo; Schlaich, Alexander; Holm, ChristianThe probability distribution of chain ends meeting when one end of the polymer is fixed to a certain distance to a reflecting wall is investigated. For an ideal polymer chain the probability distribution can be evaluated analytically via classic polymer theory. These analytical predictions are compared to atomistic MD simulations of one tethered alkane chain close to the wall. The results demonstrate that a confining wall can lead to a significant increase in the return probability for the chain ends, and thus, can increase the occurrence of ring‐closing reactions. It is further demonstrated that the excess return probability shows a maximum at a certain distance, thereby yielding an optimal catalyst position in the ring‐closing reaction.Item Open Access CO2-induced drastic decharging of dielectric surfaces in aqueous suspensions(2024) Vogel, Peter; Beyer, David; Holm, Christian; Palberg, ThomasWe study the influence of airborne CO2 on the charge state of carboxylate stabilized polymer latex particles suspended in aqueous electrolytes. We combine conductometric experiments interpreted in terms of Hessinger's conductivity model with Poisson-Boltzmann cell (PBC) model calculations with charge regulation boundary conditions. Without CO2, a minority of the weakly acidic surface groups are dissociated and only a fraction of the total number of counter-ions actually contribute to conductivity. The remaining counter-ions exchange freely with added other ions like Na+, K+ or Cs+. From the PBC-calculations we infer a corresponding pKa of 4.26 as well as a renormalized charge in reasonably good agreement with the number of freely mobile counter-ions. Equilibration of salt- and CO2-free suspensions against ambient air leads to a drastic de-charging, which exceeds by far the expected effects of to dissolved CO2 and its dissociation products. Further, no counter-ion-exchange is observed. To reproduce the experimental findings, we have to assume an effective pKa of 6.48. This direct influence of CO2 on the state of surface group dissociation explains our recent finding of a CO2-induced decrease of the ζ-potential and supports the suggestion of an additional charge regulation caused by molecular CO2. Given the importance of charged surfaces in contact with aqueous electrolytes, we anticipate that our observations bear substantial theoretical challenges and important implications for applications ranging from desalination to bio-membranes.Item Open Access An extensible lattice Boltzmann method for viscoelastic flows : complex and moving boundaries in Oldroyd-B fluids(2021) Kuron, Michael; Stewart, Cameron; de Graaf, Joost; Holm, ChristianMost biological fluids are viscoelastic, meaning that they have elastic properties in addition to the dissipative properties found in Newtonian fluids. Computational models can help us understand viscoelastic flow, but are often limited in how they deal with complex flow geometries and suspended particles. Here, we present a lattice Boltzmann solver for Oldroyd-B fluids that can handle arbitrarily shaped fixed and moving boundary conditions, which makes it ideally suited for the simulation of confined colloidal suspensions. We validate our method using several standard rheological setups and additionally study a single sedimenting colloid, also finding good agreement with the literature. Our approach can readily be extended to constitutive equations other than Oldroyd-B. This flexibility and the handling of complex boundaries hold promise for the study of microswimmers in viscoelastic fluids.Item Open Access Implicit-solvent coarse-grained simulations of linear-dendritic block copolymer micelles(2023) Brito, Mariano E.; Mikhtaniuk, Sofia E.; Neelov, Igor M.; Borisov, Oleg V.; Holm, ChristianThe design of nanoassemblies can be conveniently achieved by tuning the strength of the hydrophobic interactions of block copolymers in selective solvents. These block copolymer micelles form supramolecular aggregates, which have attracted great attention in the area of drug delivery and imaging in biomedicine due to their easy-to-tune properties and straightforward large-scale production. In the present work, we have investigated the micellization process of linear–dendritic block copolymers in order to elucidate the effect of branching on the micellar properties. We focus on block copolymers formed by linear hydrophobic blocks attached to either dendritic neutral or charged hydrophilic blocks. We have implemented a simple protocol for determining the equilibrium micellar size, which permits the study of linear–dendritic block copolymers in a wide range of block morphologies in an efficient and parallelizable manner. We have explored the impact of different topological and charge properties of the hydrophilic blocks on the equilibrium micellar properties and compared them to predictions from self-consistent field theory and scaling theory. We have found that, at higher degrees of branching in the corona and for short polymer chains, excluded volume interactions strongly influence the micellar aggregation as well as their effective charge.Item Open Access Influence of bacterial swimming and hydrodynamics on attachment of phages(2024) Lohrmann, Christoph; Holm, Christian; Datta, Sujit S.Bacteriophages (“phages”) are viruses that infect bacteria. Since they do not actively self-propel, phages rely on thermal diffusion to find target cells - but can also be advected by fluid flows, such as those generated by motile bacteria themselves in bulk fluids. How does the flow field generated by a swimming bacterium influence how it encounters phages? Here, we address this question using coupled molecular dynamics and lattice Boltzmann simulations of flagellated bacteria swimming through a bulk fluid containing uniformly-dispersed phages. We find that while swimming increases the rate at which phages attach to both the cell body and flagellar propeller, hydrodynamic interactions strongly suppress this increase at the cell body, but conversely enhance this increase at the flagellar bundle. Our results highlight the pivotal influence of hydrodynamics on the interactions between bacteria and phages, as well as other diffusible species, in microbial environments.Item Open Access Renormalized charge and dielectric effects in colloidal interactions : a numerical solution of the nonlinear Poisson-Boltzmann equation for unknown boundary conditions(2023) Schlaich, Alexander; Tyagi, Sandeep; Kesselheim, Stefan; Sega, Marcello; Holm, ChristianThe Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, introduced more than 70 years ago, is a hallmark of colloidal particle modeling. For highly charged particles in the dilute regime, it is often supplemented by Alexander’s prescription (Alexander et al. in J Chem Phys 80:5776, 1984) for using a renormalized charge. Here, we solve the problem of the interaction between two charged colloids at finite ionic strength, including dielectric mismatch effects, using an efficient numerical scheme to solve the nonlinear Poisson-Boltzmann (NPB) equation with unknown boundary conditions. Our results perfectly match the analytical predictions for the renormalized charge by Trizac and coworkers (Aubouy et al. in J Phys A 36:5835, 2003). Moreover, they allow us to reinterpret previous molecular dynamics (MD) simulation results by Kreer et al. (Phys Rev E 74:021401, 2006), rendering them now in agreement with the expected behavior. We furthermore find that the influence of polarization becomes important only when the Debye layers overlap significantly.