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From studies via molecular dynamics simulations, we report results on structure and dynamics in mixtures of active colloids and passive polymers that are confined inside a spherical container with a repulsive boundary.

Glass as a material was already known in ancient Egypt. Now its use for windows, bottles, etc. is very common; thus, it may sound surprising that the glassy state of matter and the transition from an undercooled melt to this state are grand challenge problems of physics. This article describes the basic concepts; then it points out how the discovery of “spin glasses” and the theory by Giorgio Parisi has given a new boost to the interest in these problems. The status of a theory of the glass transition will be critically discussed.

Lignin is the second most abundant biopolymer on earth and accrues in large amounts in the pulp- and paper industry. While currently lignins are mainly used for low-value applications such as energy production, recently the potential of laccases for upgrading lignins has been demonstrated. In this study, two laccases of fungal and bacterial origin were characterized regarding their potential to polymerize lignosulfonate. The laccases MaL1 from Melanocarpus albomyces, and SrLA from Streptomyces rochei were heterologously expressed and showed typical characteristics of laccases, like acidic pH optima for ABTS at pH 4 and 5, respectively, and temperature optima at 50 °C and 80 °C. Polymerization of lignosulfonate with MaL1 led to an almost two-fold increase of the molecular weight, according to size exclusion (SEC) multiangle laser light scattering (MALLS) analysis. In contrast, SrLA showed considerably less activity on lignosulfonates, as measured based on oxygen consumption and SEC-MALLS.

Conformations of wormlike chains in cylindrical pores with attractive walls are explored for varying pore radius and strength of the attractive wall potential by molecular dynamics simulations of a coarse-grained model. Local quantities such as the fraction of monomeric units bound to the surface and the bond-orientational order parameter as well as the radial density distribution are studied, as well as the global chain extensions parallel to the cylinder axis and perpendicular to the cylinder surface. A nonmonotonic convergence of these properties to their counterparts for adsorption on a planar substrate is observed due to the conflict between pore surface curvature and chain stiffness. Also the interpretation of partially adsorbed chains in terms of trains, loops, and tails is discussed.

A tutorial introduction to the statistical mechanics of phase transitions and phase coexistence is presented, starting out from equilibrium systems and nonequilibrium steady-state situations in ext...

Binary mixtures of semiflexible polymers with the same chain length, but different persistence lengths, separate into two coexisting different nematic phases when the osmotic pressure of the lyotropic solution is varied. Molecular Dynamics simulations and Density Functional Theory predict phase diagrams either with a triple point, where the isotropic phase coexists with two nematic phases or a critical point of unmixing within the nematic mixture. The difference in locally preferred bond angles between the constituents drives this unmixing without any attractive interactions between monomers.

The interplay of the isotropic-nematic transition and phase separation in lyotropic solutions of two types of semiflexible macromolecules with pronounced difference in chain stiffness is studied by Density Functional Theory and Molecular Dynamics simulations. While the width of the isotropic-nematic two-phase coexistence region is narrow for solutions with a single type of semiflexible chain, the two-phase coexistence region widens for solutions containing two types of chains with rather disparate stiffness. In the nematic phase, both types of chains contribute to the nematic order, with intermediate values of the order parameter compared to the corresponding single component solutions. As the difference in bending stiffness is increased, the two chain types separate into two coexisting nematic phases. The phase behavior is rationalized by considering the chemical potentials of the two components and the Gibbs excess free energy. The geometric properties of the chain conformations under the various conditions are also discussed.

Solutions of semiflexible polymers confined in cylindrical pores with repulsive walls are studied by Molecular Dynamics simulations for a wide range of polymer concentrations. Both the case where both lengths are of the same order and the case when the persistence length by far exceeds the contour length are considered, and the enhancement of nematic order along the cylinder axis is characterized. With increasing density the character of the surface effect changes from depletion to the formation of a layered structure. For binary 50 : 50 mixtures of the two types of polymers an interplay between surface enrichment of the stiffer component and the isotropic-nematic transition is found, and a phase separated structure with cylindrical symmetry occurs, with the isotropic phase located around the cylinder axis. For melt densities the mixed nematic phase forms at the wall a layer with a screw-like structure of a tilted smectic phase. The observed behavior is tentatively interpreted in terms of the competition of the chain orientational entropy with entropy of mixing and excluded volume due to the wall.

A model for a mixture of two kinds of semiflexible polymers (A and B) with the same chain length (NA = NB = 32), but different persistence lengths, confined between parallel planar repulsive walls in a common good solvent is studied by molecular dynamics simulations.

Two different tools for assessing pedagogical content knowledge (PCK) of mathematics teachers used in the framework of the COACTIV study are systematically compared in this paper, namely the paper-and-pencil test consisting of items on the three facets knowledge of explaining and representation, knowledge of student thinking and typical mistakes, and knowledge of the potential of mathematical tasks, and the video vignettes instrument that examines teachers' proposed continuations for presented lesson video clips specific to their subject-related and methodological competence aspects. Initially, both COACTIV PCK assessment tools are systematically contrasted for the first time with respect to their predictive validity for instructional quality (N = 163 German secondary mathematics teachers) as well as student learning gains (N = 3806 PISA students from 169 different classes) by means of path models showing that PCK, when assessed by the paper-and-pencil method, can better predict instructional quality than the video vignettes instrument can. Next, we theoretically propose the cascade model as capable of integrating pertinent theories on teacher competence and instructional quality. This model implies five 'columns' that are ordered according to a sequential causal chain (teacher disposition -> situation-specific skills -> observable teaching behavior -> student mediation -> learning gains). Finally, we specify four out of the five 'columns' of this cascade model, based empirically on the COACTIV data.

Dealing with all aspects of Monte Carlo simulation of complex physical systems encountered in condensed matter physics and statistical mechanics, this book provides an introduction to computer simulations in physics. The 5th edition contains extensive new material describing numerous powerful algorithms and methods that represent recent developments in the field. New topics such as active matter and machine learning are also introduced. Throughout, there are many applications, examples, recipes, case studies, and exercises to help the reader fully comprehend the material. This book is ideal for graduate students and researchers, both in academia and industry, who want to learn techniques that have become a third tool of physical science, complementing experiment and analytical theory.

Mixtures of semiflexible polymers with a mismatch in either their persistence lengths or their contour lengths are studied by Density Functional Theory and Molecular Dynamics simulation. Considering lyotropic solutions under good solvent conditions, the mole fraction and pressure is systematically varied for several cases of bending stiffness κ (the normalized persistence length) and chain length N. For binary mixtures with different chain length (i.e., NA=16, NB=32 or 64) but the same stiffness, isotropic-nematic phase coexistence is studied. For mixtures with the same chain length (N=32) and large stiffness disparity (κB/κA=4.9 to 8), both isotropic-nematic and nematic-nematic unmixing occur. It is found that the phase diagrams may exhibit a triple point or a nematic-nematic critical point, and that coexisting phases differ appreciably in their monomer densities. The properties of the two types of chains (nematic order parameters, chain radii, etc.) in the various phases are studied in detail, and predictions on the (anisotropic) critical behavior near the critical point of nematic-nematic unmixing are made.

Sodium chloride (NaCl) is one of the key components of atmospheric aerosols. The surface tension of aqueous NaCl solution (σNaCl,sol) and its concentration dependence are essential to determine the equilibrium water vapor pressure of aqueous NaCl droplets. Supersaturated NaCl solution droplets are observed in laboratory experiments and under atmospheric conditions, but the experimental data for σNaCl,sol are mostly limited up to subsaturated solutions. In this study, the surface tension of aqueous NaCl is investigated by molecular dynamics (MD) simulations and the pressure tensor method from dilute to highly supersaturated solutions. We show that the linear approximation of concentration dependence of σNaCl,sol at molality scale can be extended to the supersaturated NaCl solution until a molality of ∼10.7 mol kg−1 (i.e., solute mass fraction (xNaCl) of ∼0.39). Energetic analyses show that this monotonic increase in surface tension is driven by the increase in excess surface enthalpy (ΔH) as the solution becomes concentrated. After that, the simulated σNaCl,sol remains almost unchanged until xNaCl of ∼0.47 (near the concentration upon efflorescence). The existence of the “inflection point” at xNaCl of ∼0.39 and the stable surface tension of xNaCl between ∼0.39 and ∼0.47 can be attributed to the nearly unchanged excess surface entropy term (T⋅ΔS) and the excess surface enthalpy term (ΔH). After a “second inflection point” at xNaCl of ∼0.47, the simulated σNaCl,sol gradually regains the growing momentum with a tendency to approach the surface tension of molten NaCl (∼175.58 mN m−1 at 298.15 K, MD simulation-based extrapolation). This fast increase in σNaCl,sol at xNaCl>0.47 is a process driven by excess surface enthalpy and excess surface entropy. Our results reveal different regimes of concentration dependence of the surface tension of aqueous NaCl at 298.15 K: a water-dominated regime (xNaCl from 0 to ∼0.39), a transition regime (xNaCl from ∼0.39 to ∼0.47) and a molten NaCl-dominated regime (xNaCl from ∼0.47 to 1).

he contact angle of a liquid droplet on a surface under partial wetting conditions differs for a nanoscopically rough or periodically corrugated surface from its value for a perfectly flat surface. Wenzel's relation attributes this difference simply to the geometric magnification of the surface area (by a factor $r_{\rm w}$), but the validity of this idea is controversial. We elucidate this problem by model calculations for a sinusoidal corrugation of the form $z_{\rm wall}(y) = \Delta\cos(2\pi y/\lambda)$ , for a potential of short range $\sigma_{\rm w}$ acting from the wall on the fluid particles. When the vapor phase is an ideal gas, the change of the wall-vapor surface tension can be computed exactly, and corrections to Wenzel's equation are typically of order $\sigma_{\rm w}\Delta/\lambda^2$. For fixed $r_{\rm w}$ and fixed $\sigma_{\rm w}$ the approach to Wenzel's result with increasing $\lambda$ may be nonmonotonic and this limit often is only reached for $\lambda/\sigma_{\rm w}>30$. For a non-additive binary mixture, density functional theory is used to work out the density profiles of both coexisting phases both for planar and corrugated walls, as well as the corresponding surface tensions. Again, deviations from Wenzel's results of similar magnitude as in the above ideal gas case are predicted. Finally, a crudely simplified description based on the interface Hamiltonian concept is used to interpret corresponding simulation results along similar lines. Wenzel's approach is found to generally hold when $\lambda/\sigma_{\rm w}\gg 1$, $\Delta/\lambda

Size-dependent solubility is prevalent in atmospheric nanoparticles, but a molecular level understanding is still insufficient, especially for organic compounds. Here, we performed molecular dynamics simulations to investigate the size dependence of succinic acid solvation on the scale of ~1-4 nm with the potential of mean forces method. Our analyses reveal that the surface preference of succinic acid is stronger for a droplet than the slab of the same size, and the surface propensity is enhanced due to the curvature effect as the droplet becomes smaller. Energetic analyses show that such surface preference is primarily an enthalpic effect in both systems, while the entropic effect further enhances the surface propensity in droplets. On the other hand, with decreasing droplet size, the solubility of succinic acid in the internal bulk volume may decrease, imposing an opposite effect on the size dependence of solubility as compared with the enhanced surface propensity. Meanwhile, structural analyses, however, show that the surface to internal bulk volume ratio increases drastically, especially when considering the surface in respect to succinic acid, e.g., for droplet with radius of 1 nm, the internal bulk volume would be already close to zero for the succinic acid molecule.

When physicians are asked to determine the positive predictive value from the a priori probability of a disease and the sensitivity and false positive rate of a medical test (Bayesian reasoning), it often comes to misjudgments with serious consequences. In daily clinical practice, however, it is not only important that doctors receive a tool with which they can correctly judge—the speed of these judgments is also a crucial factor. In this study, we analyzed accuracy and efficiency in medical Bayesian inferences. In an empirical study we varied information format (probabilities vs. natural frequencies) and visualization (text only vs. tree only) for four contexts. 111 medical students participated in this study by working on four Bayesian tasks with common medical problems. The correctness of their answers was coded and the time spent on task was recorded. The median time for a correct Bayesian inference is fastest in the version with a frequency tree (2:55 min) compared to the version with a probability tree (5:47 min) or to the text only versions based on natural frequencies (4:13 min) or probabilities (9:59 min).The score diagnostic efficiency (calculated by: median time divided by percentage of correct inferences) is best in the version with a frequency tree (4:53 min). Frequency trees allow more accurate and faster judgments. Improving correctness and efficiency in Bayesian tasks might help to decrease overdiagnosis in daily clinical practice, which on the one hand cause cost and on the other hand might endanger patients’ safety.

When systems that can undergo phase separation between two coexisting phases in the bulk are confined in thin film geometry between parallel walls, the phase behavior can be profoundly modified. These phenomena shall be described and exemplified by computer simulations of the Asakura-Oosawa model for colloid-polymer mixtures, but applications to other soft matter systems (e.g. confined polymer blends) will also be mentioned. Typically a wall will prefer one of the phases, and hence the composition of the system in the direction perpendicular to the walls will not be homogeneous. If both walls are of the same kind, this effect leads to a distortion of the phase diagram of the system in thin film geometry, in comparison with the bulk, analogous to the phenomenon of "capillary condensation" of simple fluids in thin capillaries. In the case of "competing walls", where both walls prefer different phases of the two phases coexisting in the bulk, a state with an interface parallel to the walls gets stabilized. The transition from the disordered phase to this "soft mode phase" is rounded by the finite thickness of the film and not a sharp phase transition. However, a sharp transition can occur where this interface gets localized at (one of) the walls. The relation of this interface localization transition to wetting phenomena is discussed. Finally, an outlook to related phenomena is given, such as the effects of confinement in cylindrical pores on the phase behavior, and more complicated ordering phenomena (lamellar mesophases of block copolymers or nematic phases of liquid crystals under confinement)., Comment: 25 pages, 17 figures, to be published in Soft Matter

In the present paper we empirically investigate the psychometric properties of some of the most famous statistical and logical cognitive illusions from the “heuristics and biases” research program by Daniel Kahneman and Amos Tversky, who nearly 50 years ago introduced fascinating brain teasers such as the famous Linda problem, the Wason card selection task, and so-called Bayesian reasoning problems (e.g., the mammography task). In the meantime, a great number of articles has been published that empirically examine single cognitive illusions, theoretically explaining people’s faulty thinking, or proposing and experimentally implementing measures to foster insight and to make these problems accessible to the human mind. Yet these problems have thus far usually been empirically analyzed on an individual-item level only (e.g., by experimentally comparing participants’ performance on various versions of one of these problems). In this paper, by contrast, we examine these illusions as a group and look at the ability to solve them as a psychological construct. Based on an sample ofN= 2,643 Luxembourgian school students of age 16–18 we investigate the internal psychometric structure of these illusions (i.e., Are they substantially correlated? Do they form a reflexive or a formative construct?), their connection to related constructs (e.g., Are they distinguishable from intelligence or mathematical competence in a confirmatory factor analysis?), and the question of which of a person’s abilities can predict the correct solution of these brain teasers (by means of a regression analysis).

The adsorption transition and the structure of semiflexible adsorbed macromolecules are studied by a molecular dynamics simulation of a coarse-grained, bead-spring type model. Varying chain length N and stiffness κ (which is proportional to the persistence length lp in d = 3 dimensions) as well as the strength ϵwall of the adsorption potential, the adsorbed monomer fraction, orientational bond order parameter, and chain linear dimensions are studied. In the simulations, excluded volume interactions normally are included but can be “switched off,” and thus, the influence of excluded volume (leading to deviations from predictions of the wormlike chain model) can be identified. It is shown that the variation in the adsorption threshold ϵwallcr with lp is compatible with the predicted law ϵwallcr∝lp−1/3. In the vicinity of the adsorption threshold, the coils are still three-dimensional, and for large lp, the effect of the excluded volume is almost negligible, while for strongly adsorbed chains it is always felt. Near the transition, the decay length of orientational correlations along the chain contour increases gradually from lp to 2lp. While the latter value is expected for strictly two-dimensional chains from the Kratky–Porod model, this model is inaccurate for the description of lateral chain dimensions of long, strongly adsorbed, semiflexible polymers due to its neglect of excluded volume. The significance of these findings for the interpretation of pertinent experiments is briefly discussed.

Das aus der Kognitionspsychologie stammende Konzept der sogenannten naturlichen Haufigkeiten wird seit etwa 20 Jahren auch in der Mathematikdidaktik diskutiert. Im vorliegenden Beitrag soll illustriert werden, dass trotz der mittlerweile enormen Fulle an empirischen Studien noch zahlreiche fachdidaktische Fragestellungen unbeantwortet sind. So ist die Ersetzung von Wahrscheinlichkeiten (wie z. B. „80 %“) durch zwei absolute Haufigkeiten in der Form von naturlichen Haufigkeiten (z. B. „4 von 5“) zwar als verstandnisfordernd anerkannt, es ist aber noch unklar, wie genau sich naturliche Haufigkeiten definieren lassen, welche Eigenschaften entsprechende Verknupfungen haben, aber auch, welche Grundvorstellungen fur den verstandnisfordernden Effekt verantwortlich sein konnten. Ein drangendes Desiderat ist daruber hinaus, dass naturliche Haufigkeiten bislang zwar im Zusammenhang mit Bayesianischen Aufgabenstellungen diskutiert werden (d. h. beim Thema Wahrscheinlichkeit), aber noch nicht im Hinblick auf ihr tatsachliches Vorkommen in der Welt (d. h., beim Thema Daten). Obschon aktuelle Stromungen in der Didaktik der Stochastik nahelegen, dass gerade eine Analyse der Darstellungsformate statistischer Informationen, denen wir in der Welt begegnen, uberhaupt erst die Voraussetzung ist, um Schulerinnen und Schuler im Sinne einer statistical literacy adaquat auf eine reflektierte Teilnahme an unserer Informationsgesellschaft vorzubereiten, geschieht dies im Zusammenhang mit Daten bislang meist mit einem Fokus auf graphische Darstellungen. Im vorliegenden Artikel (a) analysieren wir numerische Darstellungen von Anteilen und Wahrscheinlichkeiten in Alltagskommunikation und Medien, (b) vergleichen diese mit entsprechenden Darstellungen im schulischen Stochastikunterricht und (c) machen konstruktive Vorschlage, wie die hierbei zu Tage tretende Diskrepanz zwischen (a) und (b) im Stochastikunterricht adressiert werden konnte. Der Schwerpunkt liegt dabei auf dem Konzept der naturlichen Haufigkeiten.

Semiflexible polymers bound to planar substrates by a short-range surface potential are studied by Molecular Dynamics simulations to clarify the extent to which these chain molecules can be considered as strictly two-dimensional. Applying a coarse-grained bead-spring model, the chain length N and stiffness &kappa, as well as the strength of the adsorption potential ϵ w a l l are varied over a wide range. The excluded-volume (EV) interactions inherent in this model can also be &ldquo, switched off&rdquo, to provide a discretized version of the Kratky&ndash, Porod wormlike chain model. We study both local order parameters (fraction f of monomers within the range of the potential, bond-orientational order parameter &eta, ) and the mean square gyration radius parallel, &lang, R g 2 &rang, | , and perpendicular, &lang, &perp, to the wall. While for strongly adsorbed chains EV has negligible effect on f and &eta, we find that &lang, | is strongly affected when the chain contour length exceeds the persistence length. Monomer coordinates in perpendicular (&perp, ) direction are correlated over the scale of the deflection length which is estimated. It is found that f , &eta, and &lang, converge to their asymptotic values with 1 / N corrections. For both weakly and strongly adsorbed chains, the distribution functions of &ldquo, loops&rdquo, &ldquo, trains&rdquo, and &ldquo, tails&rdquo, are analyzed. Some consequences pertaining to the analysis of experiments on adsorbed semiflexible polymers are pointed out.

Wetting and drying phenomena are studied for flexible and semiflexible polymer solutions via coarse-grained molecular dynamics simulations and density functional theory calculations. The study is based on the use of Young's equation for the contact angle, determining all relevant surface tensions from the anisotropy of the pressure tensor. The solvent quality (or effective temperature, equivalently) is varied systematically, while all other interactions remain unaltered. For flexible polymers, the wetting transition temperature $T_{\rm w}$ increases monotonically with chain length $N$, while the contact angle at temperatures far below $T_{\rm w}$ is independent of $N$. For semiflexible polymer solutions, $T_{\rm w}$ varies non-monotonically with the persistence length: Initially, $T_{\rm w}$ increases with increasing chain stiffness and reaches a maximum, but then a sudden drop of $T_{\rm w}$ is observed, which is associated with the isotropic-nematic transition of the system.

Rigid spheres with a short-range attractive potential are taken as a coarse-grained model of vesicles, which contain a solution of semiflexible polymers in their interior. Assuming good solvent conditions with an implicit description of the solvent, effective monomers experience bond-length and bond-angle potentials as well as excluded-volume interaction. Due to the attractive vesicle surface, phase separation occurs between a thin shell of adsorbed monomers at the surface and a rather dilute, and therefore, disordered polymer solution in the sphere interior. While at a planar attractive surface the wormlike chains would exhibit liquid crystalline (nematic and smectic) order, the curvature of the sphere frustrates this order, causing the existence of defects in the orientational order. In the dense monolayer of surface-attached polymers, the stiff chains acquire a curvature corresponding to banana-like shapes for rather small contour length, causing a local nematic order of biaxial type. These orderings are compared to related phenomena in spheres densely filled with semiflexible polymers. We complement the results obtained by Molecuar Dynamics simulations by corresponding Density Functional Theory calculations.

A recently developed method where one analyses the finite size effects associated with liquid–solid phase equilibria including vapour–crystal coexistence is briefly reviewed. It is shown that the e...

In a theoretical description of homogeneous nucleation one frequently assumes an "equilibrium" coexistence of a liquid droplet with surrounding vapor of a density exceeding that of a saturated vapor at bulk vapor-liquid two-phase coexistence. Thereby one ignores the caveat that in the thermodynamic limit, for which the vapor would be called supersaturated, such states will at best be metastable with finite lifetime, and thus not be well-defined within equilibrium statistical mechanics. In contrast, in a system of finite volume stable equilibrium coexistence of droplet and supersaturated vapor at constant total density is perfectly possible, and numerical analysis of equilibrium free energies of finite systems allows to obtain physically relevant results. In particular, such an analysis can be used to derive the dependence of the droplet surface tension γ( R) on the droplet radius R by computer simulations. Unfortunately, however, the precision of the results produced by this approach turns out to be seriously affected by a hitherto unexplained spurious dependence of γ( R) on the total volume V of the simulation box. These finite size effects are studied here for the standard Ising/lattice gas model in d = 2 dimensions and an Ising model on the face-centered cubic lattice with 3-spin interaction, lacking symmetry between vapor and liquid phases. There also the analogous case of bubbles surrounded by undersaturated liquid is treated. It is argued that (at least a large part of) the finite size effects result from the translation entropy of the droplet or bubble in the system. This effect has been shown earlier to occur also for planar interfaces for simulations in the slab geometry. Consequences for the estimation of the Tolman length are briefly discussed. In particular, we find clear evidence that in d = 2 the leading correction of the curvature-dependent interface tension is a logarithmic term, compatible with theoretical expectations, and we show that then the standard Tolman-style analysis is inapplicable.

Molecular dynamics simulations of semiflexible polymers in a good solvent reveal a dense adsorbed layer when the solution is exposed to an attractive planar wall. This layer exhibits both a nematic and a smectic phase (smA for short and smC for longer chains) with bond vectors aligned strictly parallel to the wall. The tilt angle of the smC phase increases strongly with the contour length of the polymers. The isotropic-nematic transition is a Kosterlitz-Thouless transition and also the nematic-smectic transition is continuous. Our finding demonstrates thus a two-dimensional realization of different liquid crystalline phases, ubiquitous in three dimensions, that occurs in a single monomolecular layer ordered at least over mesoscopic scales.

Semiflexible polymers under good solvent conditions interacting with attractive planar surfaces are investigated by Molecular Dynamics (MD) simulations and classical Density Functional Theory (DFT). A bead-spring type potential complemented by a bending potential is used, allowing variation of chain stiffness from completely flexible coils to rod-like polymers whose persistence length by far exceeds their contour length. Solvent is only implicitly included, monomer-monomer interactions being purely repulsive, while two types of attractive wall-monomer interactions are considered: (i) a strongly attractive Mie-type potential, appropriate for a strictly structureless wall, and (ii) a corrugated wall formed by Lennard-Jones particles arranged on a square lattice. It is found that in dilute solutions the former case leads to the formation of a strongly adsorbed surface layer, and the profile of density and orientational order in the z-direction perpendicular to the wall is predicted by DFT in nice agreement with MD. While for very low bulk densities a Kosterlitz-Thouless type transition from the isotropic phase to a phase with power-law decay of nematic correlations is suggested to occur in the strongly adsorbed layer, for larger densities a smectic-C phase in the surface layer is detected. No "capillary nematization" effect at higher bulk densities is found in this system, unlike systems with repulsive walls. This finding is attributed to the reduction of the bulk density (in the center of the slit pore) due to polymer adsorption on the attractive wall, for a system studied in the canonical ensemble. Consequently in a system with two attractive walls nematic order in the slit pore can occur only at a higher density than for a bulk system.

Conformations of partially or fully adsorbed semiflexible polymer chains are studied varying both contour length $L$, chain stiffness, $\ensuremath{\kappa}$, and the strength of the adsorption potential over a wide range. Molecular dynamics simulations show that partially adsorbed chains (with ``tails,'' surface attached ``trains,'' and ``loops'') are not described by the Kratky-Porod wormlike chain model. The crossover of the persistence length from its three-dimensional value (${\ensuremath{\ell}}_{p}$) to the enhanced value in two dimensions ($2{\ensuremath{\ell}}_{p}$) is analyzed, and excluded volume effects are identified for $L\ensuremath{\gg}{\ensuremath{\ell}}_{p}$. Consequences for the interpretation of experiments are suggested. We verify the prediction that the adsorption threshold scales as ${\ensuremath{\ell}}_{p}^{\ensuremath{-}1/3}$.

Extensive Monte Carlo simulations have been performed on an Ising ferromagnet under conditions that would lead to complete wetting in a semi-infinite system. We studied an L×L×D slab geometry with oppositely directed surface fields so that a single interface is formed and can undergo a localization-delocalization transition. Under the chosen conditions the interface position is, on average, in the middle of the slab, and its fluctuations allow a sensitive test of predictions that the effective interactions between the interface and the confining surfaces are nonlocal. The decay of distance dependent correlation functions are measured within the surface, in the middle of the slab, and between middle and the surface for slabs of varying thickness D. From Fourier transforms of these correlation functions a nonlinear correlation length is extracted, and its behavior is found to confirm theoretical predictions for D>6 lattice spacings.

The interplay of nematic order and phase separation in solutions of semiflexible polymers in solvents of variable quality is investigated by density functional theory (DFT) and molecular dynamics (MD) simulations. We studied coarse-grained models, with a bond-angle potential to control chain stiffness, for chain lengths comparable to the persistence length of the chains. We varied both the density of the monomeric units and the effective temperature that controls the quality of the implicit solvent. For very stiff chains, only a single transition from an isotropic fluid to a nematic is found, with a phase diagram of "swan-neck" topology. For less stiff chains, however, also unmixing between isotropic fluids of different concentration, ending in a critical point, occurs for temperatures above a triple point. The associated critical behavior is examined in the MD simulations and found compatible with Ising universality. Apart from this critical behavior, DFT calculations agree qualitatively with the MD simulations.

Changing the information format from probabilities into frequencies as well as employing appropriate visualizations such as tree diagrams or 2 × 2 tables are important tools that can facilitate people’s statistical reasoning. Previous studies have shown that despite their widespread use in statistical textbooks, both of those visualization types are only of restricted help when they are provided with probabilities, but that they can foster insight when presented with frequencies instead. In the present study, we attempt to replicate this effect and also examine, by the method of eye tracking, why probabilistic 2 × 2 tables and tree diagrams do not facilitate reasoning with regard to Bayesian inferences (i.e., determining what errors occur and whether they can be explained by scan paths), and why the same visualizations are of great help to an individual when they are combined with frequencies. All ten inferences of N = 24 participants were based solely on tree diagrams or 2 × 2 tables that presented either the famous “mammography context” or an “economics context” (without additional textual wording). We first asked participants for marginal, conjoint, and (non-inverted) conditional probabilities (or frequencies), followed by related Bayesian tasks. While solution rates were higher for natural frequency questions as compared to probability versions, eye-tracking analyses indeed yielded noticeable differences regarding eye movements between correct and incorrect solutions. For instance, heat maps (aggregated scan paths) of distinct results differed remarkably, thereby making correct and faulty strategies visible in the line of theoretical classifications. Moreover, the inherent structure of 2 × 2 tables seems to help participants avoid certain Bayesian mistakes (e.g., “Fisherian” error) while tree diagrams seem to help steer them away from others (e.g., “joint occurrence”). We will discuss resulting educational consequences at the end of the paper.

The backbone conformations of individual, unperturbed synthetic macromolecules have so far not been observed directly in spite of their fundamental importance to polymer physics. Here we report the dilute solution conformations of two types of linear dendronized polymers, obtained by cryogenic transmission electron stereography and tomography. The three-dimensional trajectories show that the wormlike chain model fails to adequately describe the scaling of these thick macromolecules already beyond a few nanometers in chain length, in spite of large apparent persistence lengths and long before a signature of self-avoidance appears. This insight is essential for understanding the limitations of polymer physical models, and it motivated us to discuss the advantages and disadvantages of this approach in comparison to the commonly applied scattering techniques.

Finite-size scaling for a first-order phase transition where a continuous symmetry is broken is developed using an approximation of Gaussian probability distributions with a phenomenological ``degeneracy'' factor included. Predictions are compared with data from Monte Carlo simulations of the three-dimensional, $XXZ$ Heisenberg antiferromagnet in a field in order to study the finite-size behavior on a $L\ifmmode\times\else\texttimes\fi{}L\ifmmode\times\else\texttimes\fi{}L$ simple cubic lattice for the first-order ``spin-flop'' transition between the Ising-like antiferromagnetic state and the canted, $XY$-like state. Our theory predicts that for large linear dimension $L$ the field dependence of all moments of the order parameters as well as the fourth-order cumulants exhibit universal intersections. Corrections to leading order should scale as the inverse volume. The values of these intersections at the spin-flop transition point can be expressed in terms of a factor $q$ that characterizes the relative degeneracy of the ordered phases. Our theory yields $q=\ensuremath{\pi}$, and we present numerical evidence that is compatible with this prediction. The agreement between the theory and simulation implies a heretofore unknown universality can be invoked for first-order phase transitions.

Semiflexible polymers in concentrated lyotropic solution are studied within a bead-spring model by molecular dynamics simulations, focusing on the emergence of a smectic A phase and its properties. We systematically vary the density of the monomeric units for several contour lengths that are taken smaller than the chain persistence length. The difficulties concerning the equilibration of such systems and the choice of appropriate ensemble (constant volume versus constant pressure, where all three linear dimensions of the simulation box can fluctuate independently) are carefully discussed. Using HOOMD-blue on graphics processing units, systems containing more than a million monomeric units are accessible, making it possible to distinguish the order of the phase transitions that occur. While in this model the nematic-smectic transition is continuous, the transition from the smectic phase to a related crystalline structure with true three-dimensional long-range order is clearly of first order. Further, both orientational and positional correlations of monomeric units are studied as well as the order parameters characterizing the nematic, smectic A, and crystalline phases. The analogy between smectic order and one-dimensional harmonic crystals with respect to the behavior of the structure factor is also explored. Finally, the results are put in perspective with pertinent theoretical predictions and possible experiments.

So far, we have been using the rejection Monte Carlo algorithms. To remind us, the algorithms proceed from state x to possible state \(x'\) as outlined in Algorithm 1.

In this chapter, we use the word “interface” in the sense of a boundary between coexisting bulk phases (in thermal equilibrium). An example is the interface between liquid (e.g. water) and gas phases (water vapor) but also interfaces between fluid and solid phases (e.g. water and ice) can be considered, as well as interfaces between coexisting solid phases. The generic example are “domain walls” in magnets, separating domains with opposite orientation of the magnetization, a case that can already be studied in the framework of the simple Ising model (Chaps. 2 and 3) where one has spins on the sites of a rigid perfect lattice pointing up or down.

To be specific, let us consider for the moment the problem of N atoms in a volume V at temperature T, and we wish to calculate the average of some observable A which in quantum mechanics is described by an operator Â.

Roughly at the time (1987) when the manuscript for the first three chapters of the present book was completed, several breakthroughs occurred. They had a profound influence on the scope of Monte Carlo simulations in statistical physics, particularly for the study of phase transitions in lattice models.