Thermoresponsive polymer architectures have become integral building blocks of 'smart' functional materials in modern applications. For a large range of developments, e.g., for drug delivery or nanocatalytic carrier systems, the selective adsorption and partitioning of molecules (ligands or reactants) inside the polymeric matrix are key processes that have to be controlled and tuned for the desired material function. In order to gain insights into the nanoscale structure and binding details in such systems, we here employ molecular dynamics simulations of the popular poly(Nisopropylacrylamide) (PNIPAM) polymer in explicit water in the presence of various representative solute types with focus on aromatic model reactants. We model a PNIPAM polymer chain and explore the influence of its elongation, stereochemistry, and temperature on the solute binding affinities. While we find that the excess adsorption generally raises with the size of the solute, the temperaturedependent affinity to the chains is highly solute specific and has a considerable dependence on the polymer elongation (i.e., polymer swelling state). We elucidate the molecular mechanisms of the selective binding in detail and eventually present how the results can be extrapolated to macroscopic partitioning of the solutes in swollen polymer architectures, such as hydrogels.

We present all-atom molecular dynamics computer simulations of molecular crystals of the conjugated organic molecule para-sexiphenyl (p-6P), which constitutes a popular basic molecule for optoelectronic applications. After validating single-molecule properties with ab initio calculations, we demonstrate that gradually performed simulated temperature annealing leads to the spontaneous self-assembly of p-6P molecules from the fully isotropic state into the correct roomtemperature solid crystal, with only a few percent deviation from the experimental unit-cell structure. A detailed investigation of the single crystal in anisotropic Gibbs ensemble simulations yields experimentally consistent structures and solid to liquid-crystal phase behavior over a wide temperature range, providing molecular insight into nanometer-scale structural and dynamic properties of self-assembled p-6P crystals. This study thus paves the way for future investigations of the computational description of nucleation and growth mechanisms of novel p-polyphenylene derivatives in the bulk as well as at functional interfaces or heterojunctions.

We study the long-time self-diffusion of a single conjugated organic para-sexiphenyl (p-6P) molecule physisorbed on an inorganic ZnO (101̅0) surface by means of all-atom molecular dynamics computer simulations. We find strongly anisotropic diffusion processes in which the diffusive motion along the polar [0001] direction of the surface is many orders of magnitude slower at relevant experimental temperatures than in the perpendicular direction. The observation can be rationalized by the underlying charge pattern of the electrostatically heterogeneous surface, which imposes direction-dependent energy barriers to the motion of the molecule. Furthermore, the diffusive behavior is found to be normal and Arrhenius-like, governed by thermally activated energy barrier crossings. The detailed analysis of the underlying potential energy landscape shows, however, that in general the activation barriers cannot be estimated from idealized zero-temperature trajectories but must include the conformational and positional excursion of the molecule along its pathway. Furthermore, the corresponding (Helmholtz) free energy barriers are significantly smaller than the pure energetic barriers with implications on absolute rate prediction. Our findings suggest that adequately engineered substrate charge patterns could be harvested to select desired growth modes of hybrid interfaces for optoelectronic device engineering.

We present an approach for calculating coarse-grained angle-resolved effective pair potentials for uniaxial molecules. For integrating out the intramolecular degrees of freedom we apply umbrella sampling and steered dynamics techniques in atomistically-resolved molecular dynamics (MD) computer simulations. Throughout this study we focus on disk-like molecules such as coronene. To develop the methods we focus on integrating out the van-der-Waals and intramolecular interactions, while electrostatic charge contributions are neglected. The resulting coarse-grained pair potential reveals a strong temperature and angle dependence. In the next step we fit the numerical data with various Gay-Berne-like potentials to be used in more efficient simulations on larger scales. The quality of the resulting coarse-grained results is evaluated by comparing their pair and many-body structure as well as some thermodynamic quantities self-consistently to the outcome of atomistic MD simulations of many-particle systems. We find that angle-resolved potentials are essential not only to accurately describe crystal structures but also for fluid systems where simple isotropic potentials start to fail already for low to moderate packing fractions. Further, in describing these states it is crucial to take into account the pronounced temperature dependence arising in selected pair configurations due to bending fluctuations.

In this article, we present and compare two different, coarse-grained approaches to model electrostatic interactions of disc-shaped aromatic molecules, specifically coronene. Our study builds on our previous work [T. Heinemann et al., J. Chem. Phys. 141, 214110 (2014)], where we proposed, based on a systematic coarse-graining procedure starting from the atomistic level, an anisotropic effective (Gay-Berne-like) potential capable of describing van der Waals contributions to the interaction energy. To take into account electrostatics, we introduce, first, a linear quadrupole moment along the symmetry axis of the coronene disc. The second approach takes into account the fact that the partial charges within the molecules are distributed in a ring-like fashion. We then reparametrize the effective Gay-Berne-like potential such that it matches, at short distances, the ring-ring potential. To investigate the validity of these two approaches, we perform many-particle molecular dynamics simulations, focusing on the crystalline phase (karpatite) where electrostatic interaction effects are expected to be particularly relevant for the formation of tilted stacked columns. Specifically, we investigate various structural parameters as well as the melting transition. We find that the second approach yields consistent results with those from experiments despite the fact that the underlying potential decays with the wrong distance dependence at large molecule separations. Our strategy can be transferred to a broader class of molecules, such as benzene or hexabenzocoronene.

Mass transport processes of conjugated organic molecules (COMs) on inorganic surfaces are essential elements in thin film deposition for hybrid optoelectronic devices. Defects and in particular surface step-edges dictate the molecular nucleation and growth morphology, which itself determine many physical properties of the resulting hybrid interface. Here, we explore the detailed molecular kinetics and transport rates of a single physisorbed para-sexiphenyl (p-6P) molecule crossing a step-edge (a "hetero-Ehrlich-Schwoebel barrier") on the inorganic ZnO (101[combining macron]0) surface by a combination of all-atom molecular dynamics simulations and passage time theory. We determine temperature- and charge-dependent (free) energy landscapes, position-dependent diffusion coefficients, and ultimately the mean first passage time over the step-edges. We find two completely different step-edge crossing mechanisms, the occurrence and rates of which simultaneously depend on both electrostatic and thermal molecule-surface coupling. In weakly coupled systems, the molecule crosses the step relatively quickly (in nanoseconds) by log-roll mechanisms while for strongly coupled systems, it crosses relatively slowly (in microseconds) in a strictly perpendicular fashion. In the latter process, "internal friction" from intramolecular bending and torsional degrees of freedom contribute a significant corrugation to the overall crossing barrier. Furthermore, we show that crossing pathways can also change qualitatively with step-edge height. The great complexity in hetero-barrier crossing of COMs (in contrast to simple atoms) revealed in this study has implications on the interpretation and possible control of nucleation and growth mechanisms at surface defects in hybrid systems.

For lithium–sulfur (Li–S) batteries to become competitive, they require high stability and energy density. Organosulfur polymer-based cathodes have recently shown promising performance due to their ability to overcome common limitations of Li–S batteries, such as the insulating nature of sulfur. In this study, we use a multiscale modeling approach to explore the influence of the regiochemistry of a conjugated poly­(4-(thiophene-3-yl)­benzenethiol) (PTBT) polymer on its aggregation behavior and charge transport. Classical molecular dynamics simulations of the self-assembly of polymer chains with different regioregularity show that a head-to-tail/head-to-tail regularity can form a well-ordered crystalline phase of planar chains allowing for fast charge transport. Our X-ray diffraction measurements, in conjunction with our predicted crystal structure, confirm the presence of crystalline phases in the electropolymerized PTBT polymer. We quantitatively describe the charge transport in the crystalline phase in a band-like regime. Our results give detailed insights into the interplay between microstructural and electrical properties of conjugated polymer cathode materials, highlighting the effect of polymer chain regioregularity on its charge transport properties.

The quantitative role of entropy in the surface diffusion of molecules with many degrees of freedom is still not well understood. Here, we quantify entropic diffusion barriers as well as attempt frequencies by performing a systematic decomposition of the Arrhenius equation for single oligophenyl molecules of various lengths (two to six phenyl rings and benzene as the reference) on an amorphous silica surface using extensive molecular dynamics simulations. Attempt frequencies evaluated from velocity auto-correlation functions are found close to kBT/h, the frequency factor of transition state theory. Importantly, we find large positive entropy contributions to the free energy barrier of diffusion up to 55%, increasing with molecular length with 4.1 kJ/mol/phenyl ring. The entropic barrier is about 40%–60% of the entropy of the molecule surface adsorption free energy, revealing that at the transition states, the molecules can liberate a major part of their conformational states, increasing with length. The substantial role of the internal degrees of freedom for the diffusive dynamics is explicitly demonstrated by studying internally constrained, “rigid” version of the molecules. Finally, we discuss also rotational diffusion and the role of surface vibrations. Our results affirm that it is essential for quantitative studies and interpretation of surface diffusion of complex molecules to consider internal entropic effects.