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We critically examine a broad class of explicitly polarizable soft solvent models aimed at applications in dissipative particle dynamics. We obtain the dielectric permittivity using the fluctuating box dipole method in linear response theory and verify the models in relation to several test cases, including demonstrating ion desorption from an oil–water interface due to image charge effects. We additionally compute the Kirkwood factor and find that it uniformly lies in the range g K ≃ 0.7 –0.8, indicating that dipole–dipole correlations are not negligible in these models. This is supported by the measurements of dipole–dipole correlation functions. As a consequence, Onsager theory over-predicts the dielectric permittivity by 20%–30%. The mean square molecular dipole moment can be accurately estimated with a first-order Wertheim perturbation theory. [ABSTRACT FROM AUTHOR]

There is an ever increasing use of local density dependent potentials in the mesoscale modeling of complex fluids. Questions remain, though, about the dependence of the thermodynamic and structural properties of such systems on the cutoff distance used to calculate these local densities. These questions are particularly acute when it comes to the stability and structure of the vapor/liquid interface. In this article, we consider local density dependent potentials derived from an underlying van der Waals equation of state. We use simulation and density functional theory to examine how the bulk thermodynamic and interfacial properties vary with the cutoff distance, rc, used to calculate the local densities. We show quantitatively how the simulation results for bulk thermodynamic properties and vapor–liquid equilibrium approach the van der Waals limit as rc increases and demonstrate a scaling law for the radial distribution function in the large rc limit. We show that the vapor–liquid interface is stable with a well-defined surface tension and that the interfacial density profile is oscillatory, except for temperatures close to critical. Finally, we show that in the large rc limit, the interfacial tension is proportional to rc and, therefore, unlike the bulk thermodynamic properties, does not approach a constant value as rc increases. We believe that these results give new insights into the properties of local density dependent potentials, in particular their unusual interfacial behavior, which is relevant for modeling complex fluids in soft matter. [ABSTRACT FROM AUTHOR]

For industrial applications of self-assembled wormlike micelles, measurement and characterization of a micellar material's microstructure and rheology are paramount for the development and deployment of new high-performing and cost-effective formulations. Within this workflow, there are significant bottlenecks associated with experimental delays and a lack of transferability of results from one chemistry to another. In this work, we outline a process to predict microscopic and thermodynamic characteristics of wormlike micelles directly from rheological data by combining a more robust and efficient fitting algorithm with a recently published constitutive model called the Toy Shuffling model [J. D. Peterson and M. E. Cates, J. Rheol. 64, 1465–1496 (2020) and J. D. Peterson and M. E. Cates, J. Rheol. 65, 633–662 (2021)]. To support this work, linear rheology measurements were taken for 143 samples comprising a common base formulation of commercial sodium lauryl ether sulfate, cocamidopropyl betaine, and salt (NaCl). The steady state zero shear viscosity evident in linear rheology was measured in duplicate via direct steady and oscillatory shear experiments. Fitting the collected data to the model, we found trends in the microstructural and thermodynamic characteristics that agree with molecular dynamics simulations. These trends validate our new perspective on the parameters that inform the study of the relationship between chemical formulation and rheology. This work, when implemented at scale, can potentially be used to inform and test strategies for predicting self-assembled micellar structures based on chemical formulation. [ABSTRACT FROM AUTHOR]

The structure and energetics of the axial and equatorial anomers of 4,6-dimethyl-2-methoxytetrahydropyran in aqueous solutions and the preferential solvation of the equatorial form were investigated using several models. Results revealed that both quantum mechanical and continuum models can successfully predict the preferential solvation, but not the differential solvation. The classical reference interaction site model was found to successfully predict the differential solvation.

The transition path sampling (TPS) method is a powerful approach to study chemical reactions or transitional properties on complex potential energy landscapes. One of the main advantages of the method over potential of mean force methods is that reaction rates can be directly accessed without knowledge of the exact reaction coordinate. We have investigated the complementary nature of these two differing approaches, comparing transition path sampling with the weighted histogram analysis method to study a conformational change in a small model system. In this case study, the transition paths for a transition between two rotational conformers of a model disaccharide molecule, methyl β-D-maltoside, were compared with a free energy surface constrained by the two commonly used glycosidic ([lowercase_phi_synonym],ψ) torsional angles. The TPS method revealed a reaction channel that was not apparent from the potential of mean force method, and the suitability of [lowercase_phi_synonym] and ψ as reaction coordinates to describe the isomerization in vacuo was confirmed by examination of the transition path ensemble. Using both transition state theory and transition path sampling methods, the transition rate was estimated. We have estimated a characteristic time between transitions of approximately 160 ns for this rare isomerization event between the two conformations of the carbohydrate. We conclude that transition path sampling can extract subtle information about the dynamics not apparent from the potential of mean force method. However, in calculating the reaction rate, the transition path sampling method required 27.5 times the computational effort than was needed by the potential of mean force method. [ABSTRACT FROM AUTHOR]

We use a polarizable continuum approach to study the acidity of tert-butyl alcohol in water at ambient, near-critical, and supercritical conditions. In the most straightforward calculation, the bare ionic species (the tert-butoxy anion and the hydronium cation) are placed in cavities surrounded by a dielectric continuum, using a dielectric constant corresponding to the state point. A second method is first to solvate these ions with a small number of explicit water molecules and then surround this cluster with the dielectric. This is the cluster-continuum approach. We discuss the advantages and disadvantages of these two schemes and we also discuss various ways in which the second method can be implemented. No method showed quantitative agreement with all available experimental results but the first, straightforward method was the most successful in predicting the correct trends. From both a numerical and a theoretical point of view, we believe this is the method of choice. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present a molecular simulation method that yields simultaneously the equilibrium pitch wave number q and the twist elastic constant K[sub 2] of a chiral nematic liquid crystal by sampling the torque density. A simulation of an untwisted system in periodic boundary conditions gives the product K[sub 2]q; a further simulation with a uniform twist applied provides enough information to separately determine the two factors. We test our new method for a model potential, comparing the results with K[sub 2]q from a thermodynamic integration route, and with K[sub 2] from an order fluctuation analysis. We also present a thermodynamic perturbation theory analysis valid in the limit of weak chirality. [ABSTRACT FROM AUTHOR]

Presents the results concerning the structure and energetics of the cluster F[sup -](H[sub 2]O)[sub 4] using high quality ab initio methods at 0 K and an ab initio Monte Carlo simulation at 300 K. Correlation of the global energy minimum to three waters solvating the fluoride ion; Energy of structures involving four waters hydrogen bonding to the fluoride.

A kinetic theory for the frequency-dependent shear viscosity &neta;(ω) of isotropic fluids, composed of non-spherical hard convex bodies, is extended in two ways. First, the theory is reformulated to allow &neta;(ω) to be expressed directly in terms of matrix elements involving the shear stress tensor rather than in terms of the transverse momentum correlation function. Second, relaxation of the antisymmetric component of the stress, due to coupling with spin angular momentum, is explicitly incorporated; this corrects an error in a previous version of the theory. The revised kinetic theory is compared with computer simulations for hard ellipsoids of revolution of axial ratio 2, 3, 5 and 10. Both the symmetric and antisymmetric contributions to &neta;(ω) are well reproduced. Coupling with the collective molecular second-rank orientation tensor remains an important factor in determining the variation of &neta;(ω) from high to low frequencies; the prediction of the magnitude of the associated dip in &neta;(ω) is significantly improved. The new version of the theory is also more successful in predicting values of the zero-frequency shear viscosity h, the shear-orientation coupling parameter R, and the Stokes-Einstein (-Debye) products D[SUBs]&neta; and D[SUBr] &neta;. [ABSTRACT FROM AUTHOR]