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Colloids can acquire a dipolar interaction in the presence of an external AC electric field. At high field strength, the particles form strings in the field direction. However, at weaker field strength, competition with isotropic interactions is expected. One means to investigate this interplay between dipolar and isotropic interactions is to consider clusters of such particles. Therefore, we have identified, using the GMIN basin-hopping tool, a rich library of lowest energy clusters of a dipolar colloidal system, where the dipole orientation is fixed to lie along the z axis and the dipole strength is varied for m-membered clusters of 7 ≤ m ≤ 13. In the regime where the isotropic and dipolar interactions are comparable, we find elongated polytetrahedral, octahedral, and spiral clusters as well as a set of non-rigid clusters, which emerge close to the transition to strings. We further implement a search algorithm that identifies these minimum energy clusters in bulk systems using the topological cluster classification [J. Chem. Phys. 139 234506 (2013)]. We demonstrate this methodology with computer simulations, which show instances of these clusters as a function of dipole strength. [ABSTRACT FROM AUTHOR]

We investigate the phase ordering (pattern formation) of systems of two-dimensional core–shell particles using Monte Carlo (MC) computer simulations and classical density functional theory (DFT). The particles interact via a pair potential having a hard core and a repulsive square shoulder. Our simulations show that on cooling, the liquid state structure becomes increasingly characterized by long wavelength density modulations and on further cooling forms a variety of other phases, including clustered, striped, and other patterned phases. In DFT, the hard core part of the potential is treated using either fundamental measure theory or a simple local density approximation, whereas the soft shoulder is treated using the random phase approximation. The different DFTs are benchmarked using large-scale grand-canonical-MC and Gibbs-ensemble-MC simulations, demonstrating their predictive capabilities and shortcomings. We find that having the liquid state static structure factor S(k) for wavenumber k is sufficient to identify the Fourier modes governing both the liquid and solid phases. This allows us to identify from easier-to-obtain liquid state data the wavenumbers relevant to the periodic phases and to predict roughly where in the phase diagram these patterned phases arise. [ABSTRACT FROM AUTHOR]

Motion in bounded domains is a fundamental concept in various fields, including billiard dynamics and random walks on finite lattices, and has important applications in physics, ecology, and biology. An important universal property related to the average return time to the boundary, the Mean Path Length Theorem (MPLT), has been proposed theoretically and experimentally confirmed in various contexts. We investigated a wide range of mechanisms that lead to deviations from this universal behavior, such as boundary effects, reorientation, and memory processes. This study investigates the dynamics of run-and-tumble particles within a confined two-dimensional circular domain. Through a combination of theoretical approaches and numerical simulations, we validate the MPLT under uniform and isotropic particle inflow conditions. This research demonstrates that although the MPLT is generally applicable for different step length distributions, deviations occur for non-uniform angular distributions, non-elastic boundary conditions, or memory processes. These results underline the crucial influence of boundary interactions and angular dynamics on the behavior of particles in confined spaces. Our results provide new insights into the geometry and dynamics of motion in confined spaces and contribute to a better understanding of a broad spectrum of phenomena ranging from the motion of bacteria to neutron transport. This type of analysis is crucial in situations where inhomogeneity occurs, such as multiple real-world scenarios within a limited domain. [ABSTRACT FROM AUTHOR]

Microbial communities exhibit complex behaviors driven by species interactions and individual characteristics. In this study, we delve into the dynamics of a mixed bacterial population comprising two distinct species with different morphology and motility aspects. Employing agent-based modeling and computer simulations, we analyze the impacts of size ratios and packing fractions on dispersal patterns, aggregate formation, clustering, and spatial ordering. Notably, we find that motility and anisotropy of elongated bacteria significantly influence the distribution and spatial organization of nonmotile spherical species. Passive spherical cells display a superdiffusive behavior, particularly at larger size ratios in the ballistic regime. As the size ratio increases, clustering of passive cells is observed, accompanied by enhanced alignment and closer packing of active cells in the presence of higher passive cell area fractions. In addition, we identify the pivotal role of passive cell area fraction in influencing the response of active cells toward nematicity, with its dependence on size ratio. These findings shed light on the significance of morphology and motility in shaping the collective behavior of microbial communities, providing valuable insights into complex microbial behaviors with implications for ecology, biotechnology, and bioengineering. [ABSTRACT FROM AUTHOR]

In this work, the tetrahydrofuran (THF) hydrate–water interfacial free energy is determined at 500 bar, at one point of the univariant two-phase coexistence line of the THF hydrate, by molecular dynamics simulation. The mold integration–host methodology, an extension of the original mold integration technique to deal with hydrate–fluid interfaces, is used to calculate the interfacial energy. Water is described using the well-known TIP4P/Ice model, and THF is described using a rigid version of the TraPPE model. We have recently used the combination of these two models to accurately describe the univariant two-phase dissociation line of the THF hydrate in a wide range of pressures from computer simulation [Algaba et al., J. Chem. Phys. 160, 164718 (2024)]. The THF hydrate–water interfacial free energy predicted in this work is compared with the only experimental data available in the literature. The value obtained, 27(2) mJ/m2, is in excellent agreement with the experimental data taken from the literature, 24(8) mJ/m2. To the best of our knowledge, this is the first time that the THF hydrate–water interfacial free energy is predicted from computer simulation. This work confirms that the mold integration technique can be used with confidence to predict the solid–fluid interfaces of complex structures, including hydrates that exhibit sI and sII crystallographic structures. [ABSTRACT FROM AUTHOR]

The motional narrowing effect has been extensively studied for cavity exciton–polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior and (2) the asymmetric linewidths for the upper polariton and the lower polariton. However, a minimal theoretical model that is clear and adequate to address all these effects as well as the linewidth scaling relations remains missing. In this work, based on the single mode 1D Holstein–Tavis–Cummings (HTC) model, we studied the motional narrowing effect of the polariton linear absorption spectra via both semi-analytic derivations and numerically exact quantum dynamics simulations using the hierarchical equations of motion approach. The results reveal that under collective light–matter coupling between a cavity mode and N molecules, the polariton linewidth scales as 1 / N under the slow limit, while scales as 1/N under the fast limit, due to the polaron decoupling effect. Furthermore, by varying the detunings, the polariton linewidths exhibit significant motional narrowing, covering both characters mentioned above. Our analytic linewidth expressions [Eqs. (34) and (35)] agree well with the numerical exact simulations in all the parameter regimes we explored. These results indicate that the physics of motional narrowing is adequately accounted for by the single-mode 1D HTC model. We envision that both the numerical results and the analytic polariton linewidths expression presented in this work will offer great theoretical value for providing a better understanding of the exciton–polariton motional narrowing based on the HTC model. [ABSTRACT FROM AUTHOR]

In this work, we determine the dissociation line of the nitrogen (N2) hydrate by computer simulation using the TIP4P/Ice model for water and the TraPPE force field for N2. This work is the natural extension of Paper I, in which the dissociation temperature of the N2 hydrate has been obtained at 500, 1000, and 1500 bar [Algaba et al., J. Chem. Phys. 159, 224707 (2023)] using the solubility method and assuming single occupancy. We extend our previous study and determine the dissociation temperature of the N2 hydrate at different pressures, from 500 to 4500 bar, taking into account the single and double occupancy of the N2 molecules in the hydrate structure. We calculate the solubility of N2 in the aqueous solution as a function of temperature when it is in contact with a N2-rich liquid phase and when in contact with the hydrate phase with single and double occupancy via planar interfaces. Both curves intersect at a certain temperature that determines the dissociation temperature at a given pressure. We observe a negligible effect of occupancy on the dissociation temperature. Our findings are in very good agreement with the experimental data taken from the literature. We have also obtained the driving force for the nucleation of the hydrate as a function of temperature and occupancy at several pressures. As in the case of the dissociation line, the effect of occupancy on the driving force for nucleation is negligible. To the best of our knowledge, this is the first time that the effect of the occupancy on the driving force for nucleation of a hydrate that exhibits sII crystallographic structure is studied from computer simulation. [ABSTRACT FROM AUTHOR]

It has been recently shown that 2D systems can exhibit crystalline phases with long-range translational order showcasing a striking violation of the Hohenberg–Mermin–Wagner (HMW) theorem, which is valid at equilibrium. This is made possible by athermal driving mechanisms that inject energy into the system without exciting long wavelength modes of the density field, thereby inducing hyperuniformity. However, as thermal fluctuations are superimposed on the non-equilibrium driving, long-range translational order is inevitably lost. Here, we discuss the possibility of exploiting non-equilibrium effects to suppress arbitrarily large density fluctuations even when a global thermal bath is coupled to the system. We introduce a model of a harmonic crystal driven both by a global thermal bath and by a momentum conserving noise, where the typical observables related to density fluctuations and long-range translational order can be analytically derived and put in relation. This model allows us to rationalize the violation of the HMW theorem observed in previous studies through the prediction of large-wavelength phonons, which thermalize at a vanishing effective temperature when the global bath is switched off. The conceptual framework introduced through this theory is then applied to numerical simulations of a hard-disk solid in contact with a thermal bath and driven out-of-equilibrium by active collisions. Our numerical analysis demonstrates how varying driving and dissipative parameters can lead to an arbitrary enhancement of the quasi-long-range order in the system regardless of the applied global noise amplitude. Finally, we outline a possible experimental procedure to apply our results to a realistic granular system. [ABSTRACT FROM AUTHOR]

Spontaneous gas-bubble nucleation in weak gas–liquid solutions has been a challenging topic in theory, experimentation, and computer simulations. In analogy with recent advances in crystallization and droplet formation studies, the diffusive-shielding stabilization and thermodynamic irreversibility of bulk nanobubble (bNB) mechanisms are revisited and deployed to characterize nucleation processes in a stochastic framework of computer experiments using the large-scale atomic/molecular massively parallel simulator code. Theoretical bases, assumptions, and limitations underlying the irreversibility hypothesis of bNBs, and their computational counterparts, are extensively described and illustrated. In essence, it is established that the irreversibility hypothesis can be numerically investigated by converging the system volume (due to the finiteness of interatomic forces) and the initial dissolved-gas concentration in the solution (due to the single-bNB limitation). Helium nucleation in liquid Pb17Li alloy is selected as a representative case study, where it exhibits typical characteristics of noble-gas/liquid-metal systems. The proposed framework lays down the bases on which the stability of gas-bNBs in weak and supersaturated gas–liquid solutions can be inferred and explained from a novel perspective. In essence, it stochastically marches toward a unique irreversible state along out-of-equilibrium nucleation/growth trajectories. Moreover, it does not attempt to characterize the interface or any interface-related properties, neither theoretically nor computationally. It was concluded that bNBs of a few tens of He-atoms are irreversible when dissolved-He concentrations in the weak gas–liquid solution are at least ∼50 and ∼105 mol m−3 at 600 and 1000 K (and ∼ 80 MPa), respectively, whereas classical molecular dynamics -estimated solubilities are at least two orders of magnitude smaller. [ABSTRACT FROM AUTHOR]

We present a technique for measuring the interactions between pairs of colloidal particles in two optical traps. This method is particularly suitable for measuring strongly attractive potentials, an otherwise challenging task. The interaction energy is calculated from the distribution of inter-particle separations by accounting for the contribution from the optical traps with arbitrary trap profiles. The method is simple to implement and applicable to different types of pair potentials and optical trapping geometries. We apply the method to measure dipolar pair interactions in experiments with paramagnetic colloids in external magnetic fields. We obtain consistent and accurate results in all regimes, from strongly attractive to repulsive potentials. By means of computer simulations, we demonstrate that the proposed method can be successfully applied to systems with complex pair interactions characterized by multiple attractive and repulsive regimes, which are ubiquitous in soft and biological matter. [ABSTRACT FROM AUTHOR]

The celebrated generalized Stokes law predicts that the velocity of a particle pulled through a liquid by an external force, Fex, is directly proportional to the force and inversely proportional to the friction ζ acted by the medium on the particle. We investigate the range of validity of the generalized Stokes law at molecular length scales by employing computer simulations to calculate friction by pulling a tagged particle with a constant force. We thus calculate friction for two model interaction potentials, Lennard-Jones and soft sphere, for several particle sizes, ranging from radius (a) smaller than the solvent particles to three times larger. We next obtain friction from diffusion (D) by using Einstein's relation between diffusion and friction ζ in an unperturbed liquid. We find a quantitative agreement between the two at a small-to-intermediate pulling force regime for all the sizes studied. The law does break down at a large pulling force beyond a threshold value. Importantly, the range of validity of Stokes' scheme to obtain friction increases substantially if we turn off the attractive part of the interaction potential. Additionally, we calculate the viscosity (η) of the unperturbed liquid and find a good agreement with the Stokes–Einstein relation ζ = Cηa for the viscosity dependence with a value of C close to 5 π, which is intermediate between the slip and stick boundary condition. [ABSTRACT FROM AUTHOR]

In this work, the effect of the range of dispersive interactions in determining the three-phase coexistence line of the CO2 and CH4 hydrates has been studied. In particular, the temperature (T3) at which solid hydrate, water, and liquid CO2/gas CH4 coexist has been determined through molecular dynamics simulations using different cutoff values (from 0.9 to 1.6 nm) for dispersive interactions. The T3 of both hydrates has been determined using the direct coexistence simulation technique. Following this method, the three phases in equilibrium are put together in the same simulation box, the pressure is fixed, and simulations are performed at different temperatures T. If the hydrate melts, then T > T3. Conversely, if the hydrate grows, then T < T3. The effect of the cutoff distance on the dissociation temperature has been analyzed at three different pressures for CO2 hydrate: 100, 400, and 1000 bar. Then, we have changed the guest and studied the effect of the cutoff distance on the dissociation temperature of the CH4 hydrate at 400 bar. Moreover, the effect of long-range corrections for dispersive interactions has been analyzed by running simulations with homo- and inhomogeneous corrections and a cutoff value of 0.9 nm. The results obtained in this work highlight that the cutoff distance for the dispersive interactions affects the stability conditions of these hydrates. This effect is enhanced when the pressure is decreased, displacing the T3 about 2–4 K depending on the system and the pressure. [ABSTRACT FROM AUTHOR]

In this work, the effects of finite size on the determination of the three-phase coexistence temperature (T3) of the carbon dioxide (CO2) hydrate have been studied by molecular dynamic simulations and using the direct coexistence technique. According to this technique, the three phases involved (hydrate–aqueous solution–liquid CO2) are placed together in the same simulation box. By varying the number of molecules of each phase, it is possible to analyze the effect of simulation size and stoichiometry on the T3 determination. In this work, we have determined the T3 value at 8 different pressures (from 100 to 6000 bar) and using 6 different simulation boxes with different numbers of molecules and sizes. In two of these configurations, the ratio of the number of water and CO2 molecules in the aqueous solution and the liquid CO2 phase is the same as in the hydrate (stoichiometric configuration). In both stoichiometric configurations, the formation of a liquid drop of CO2 in the aqueous phase is observed. This drop, which has a cylindrical geometry, increases the amount of CO2 available in the aqueous solution and can in some cases lead to the crystallization of the hydrate at temperatures above T3, overestimating the T3 value obtained from direct coexistence simulations. The simulation results obtained for the CO2 hydrate confirm the sensitivity of T3 depending on the size and composition of the system, explaining the discrepancies observed in the original work by Míguez et al. [J. Chem Phys. 142, 124505 (2015)]. Non-stoichiometric configurations with larger unit cells show a convergence of T3 values, suggesting that finite-size effects for these system sizes, regardless of drop formation, can be safely neglected. The results obtained in this work highlight that the choice of a correct initial configuration is essential to accurately estimate the three-phase coexistence temperature of hydrates by direct coexistence simulations. [ABSTRACT FROM AUTHOR]

In this work, the univariant two-phase coexistence line of the tetrahydrofuran (THF) hydrate is determined from 100 to 1000 bar by molecular dynamics simulations. This study is carried out by putting in contact a THF hydrate phase with a stoichiometric aqueous solution phase. Following the direct coexistence technique, the pressure is fixed, and the coexistence line is determined by analyzing if the hydrate phase grows or melts at different values of temperature. Water is described using the well-known TIP4P/Ice model. We have used two different models of THF based on the transferable parameters for phase equilibria-united atom approach (TraPPE-UA), the original (flexible) TraPPe-UA model and a rigid and planar version of it. Overall, at high pressures, small differences are observed in the results obtained by both models. However, large differences are observed in the computational efforts required by the simulations performed using both models, being the rigid and planar version much faster than the original one. The effect of the unlike dispersive interactions between the water and THF molecules is also analyzed at 250 bar using the rigid and planar THF model. In particular, we modify the Berthelot combining rule via a parameter ξO-THF that controls the unlike water–THF dispersive interactions. We analyze the effect on the dissociation temperature of the hydrate when ξO-THF is modified from 1.0 (original Berthelot combining rule) to 1.4 (modified Berthelot combining rule). We use the optimized value ξO-THF = 1.4 and the rigid THF model in a transferable way to predict the dissociation temperatures at other pressures. We find excellent agreement between computer simulation predictions and experimental data taken from the literature. [ABSTRACT FROM AUTHOR]

Clathrate hydrates are vital in energy research and environmental applications. Understanding their stability is crucial for harnessing their potential. In this work, we employ direct coexistence simulations to study finite-size effects in the determination of the three-phase equilibrium temperature (T3) for methane hydrates. Two popular water models, TIP4P/Ice and TIP4P/2005, are employed, exploring various system sizes by varying the number of molecules in the hydrate, liquid, and gas phases. The results reveal that finite-size effects play a crucial role in determining T3. The study includes nine configurations with varying system sizes, demonstrating that smaller systems, particularly those leading to stoichiometric conditions and bubble formation, may yield inaccurate T3 values. The emergence of methane bubbles within the liquid phase, observed in smaller configurations, significantly influences the behavior of the system and can lead to erroneous temperature estimations. Our findings reveal finite-size effects on the calculation of T3 by direct coexistence simulations and clarify the system size convergence for both models, shedding light on discrepancies found in the literature. The results contribute to a deeper understanding of the phase equilibrium of gas hydrates and offer valuable information for future research in this field. [ABSTRACT FROM AUTHOR]

Designing homogeneous networks is considered one typical strategy for solving the problem of strength and toughness conflict of polymer network materials. Experimentalists have proposed the hypothesis of obtaining a structurally homogeneous hydrogel by crosslinking tetra-armed polymers, whose homogeneity was claimed to be verified by scattering characterization and other methods. Nevertheless, it is highly desirable to further evaluate this issue from other perspectives. In this study, a coarse-grained molecular dynamics simulation coupled with a stochastic reaction model is applied to reveal the topological structure of a polymer network synthesized by tetra-armed monomers as precursors. Two different scenarios, distinguished by whether internal cross-linking is allowed, are considered. We introduce the Dijkstra algorithm from graph theory to precisely characterize the network structure. The microscopic features of the network structure, e.g., loop size, dispersity, and size distribution, are obtained via the Dijkstra algorithm. By comparing the two reaction scenarios, Scenario II exhibits an overall more idealized structure. Our results demonstrate the feasibility of the Dijkstra algorithm for precisely characterizing the polymer network structure. We expect this work will provide a new insight for the evaluation and description of gel networks and further help to reveal the dynamic process of network formation. [ABSTRACT FROM AUTHOR]

Computer simulation has long been an essential partner of ultrafast experiments, allowing the assignment of microscopic mechanistic detail to low-dimensional spectroscopic data. However, the ability of theory to make a priori predictions of ultrafast experimental results is relatively untested. Herein, as a part of a community challenge, we attempt to predict the signal of an upcoming ultrafast photochemical experiment using state-of-the-art theory in the context of preexisting experimental data. Specifically, we employ ab initio Ehrenfest with collapse to a block mixed quantum–classical simulations to describe the real-time evolution of the electrons and nuclei of cyclobutanone following excitation to the 3s Rydberg state. The gas-phase ultrafast electron diffraction (GUED) signal is simulated for direct comparison to an upcoming experiment at the Stanford Linear Accelerator Laboratory. Following initial ring-opening, dissociation via two distinct channels is observed: the C3 dissociation channel, producing cyclopropane and CO, and the C2 channel, producing CH2CO and C2H4. Direct calculations of the GUED signal indicate how the ring-opened intermediate, the C2 products, and the C3 products can be discriminated in the GUED signal. We also report an a priori analysis of anticipated errors in our predictions: without knowledge of the experimental result, which features of the spectrum do we feel confident we have predicted correctly, and which might we have wrong? [ABSTRACT FROM AUTHOR]

The impact of successive replacement of K+ by Na+ on the megahertz–gigahertz polarization response of 0.25[fKSCN + (1 − f)NaSCN] + 0.75CH3CONH2 deep eutectic solvents (DESs) was explored via temperature-dependent (303 ≤ T/K ≤ 343) dielectric relaxation (DR) measurements and computer simulations. Both the DR measurements (0.2 ≤ ν/GHz ≤ 50) and the simulations revealed multi-Debye relaxations accompanied by a decrease in the solution static dielectric constant (ɛs) upon the replacement of K+ by Na+. Accurate measurements of the DR response of DESs below 100 MHz were limited by the well-known one-over-frequency divergence for conducting solutions. This problem was tackled in simulations by removing the zero frequency contributions arising from the ion current to the total simulated DR response. The temperature-dependent measurements revealed a much stronger viscosity decoupling of DR times for Na+-containing DES than for the corresponding K+ system. The differential scanning calorimetry measurements indicated a higher glass transition temperature for Na+-DES (∼220 K) than K+-DES (∼200 K), implying more fragility and cooperativity for the former (Na+-DES) than the latter. The computer simulations revealed a gradual decrease in the average number of H bonds (⟨nHB⟩) per acetamide molecule and increased frustrations in the average orientational order upon the replacement of K+ by Na+. Both the measured and simulated ɛs values were found to decrease linearly with ⟨nHB⟩. Decompositions of the simulated DR spectra revealed that the cation-dependent cross interaction (dipole-ion) term contributes negligibly to ɛs and appears in the terahertz regime. Finally, the simulated collective single-particle reorientational relaxations and the structural H-bond fluctuation dynamics revealed the microscopic origin of the cation identity dependence shown by the measured DR relaxation times. [ABSTRACT FROM AUTHOR]

Biological lipid membranes are generally asymmetric, not only with respect to the composition of the two membrane leaflets but also with respect to the state of mechanical stress on the two sides. Computer simulations of such asymmetric membranes pose unique challenges with respect to the choice of boundary conditions and ensemble in which such simulations are to be carried out. Here, we demonstrate an alternative to the usual choice of fully periodic boundary conditions: The membrane is only periodic in one direction, with free edges running parallel to the single direction of periodicity. In order to maintain bilayer asymmetry under these conditions, nanoscale "sticky tapes" are adhered to the membrane edges in order to prevent lipid flip-flop across the otherwise open edge. In such semi-periodic simulations, the bilayer is free to choose both its area and mean curvature, allowing for minimization of the bilayer elastic free energy. We implement these principles in a highly coarse-grained model and show how even the simplest examples of such simulations can reveal useful membrane elastic properties, such as the location of the monolayer neutral surface. [ABSTRACT FROM AUTHOR]

The ice surface is known for presenting a very small kinetic friction coefficient, but the origin of this property remains highly controversial to date. In this work, we revisit recent computer simulations of ice sliding on atomically smooth substrates, using newly calculated bulk viscosities for the TIP4P/ice water model. The results show that spontaneously formed premelting films in static conditions exhibit an effective viscosity that is about twice the bulk viscosity. However, upon approaching sliding speeds in the order of m/s, the shear rate becomes very large, and the viscosities decrease by several orders of magnitude. This shows that premelting films can act as an efficient lubrication layer despite their small thickness and illustrates an interesting interplay between confinement enhanced viscosities and shear thinning. Our results suggest that the strongly thinned viscosities that operate under the high speed skating regime could largely reduce the amount of frictional heating. [ABSTRACT FROM AUTHOR]

The operations of current quantum computers are still significantly affected by decoherence caused by interaction with the environment. In this work, we employ the non-perturbative hierarchical equations of motion (HEOM) method to simulate the operation of model quantum computers and reveal the effects of dissipation on the entangled quantum states and on the performance of well-known quantum algorithms. Multi-qubit entangled states in Shor's factorizing algorithm are first generated and propagated using the HEOM. It is found that the failure of factorization is accompanied by a loss of fidelity and mutual information. An important challenge in using the HEOM to simulate quantum computers in a dissipative environment is how to efficiently treat systems with many qubits. We propose a two-dimensional tensor network scheme for this problem and demonstrate its capability by simulating a one-dimensional random circuit model with 21 qubits. [ABSTRACT FROM AUTHOR]

Polymer blends are critical in many commercial products and industrial processes and their phase behavior is therefore of paramount importance. In most circumstances, such blends are formulated with samples of high dispersity, which have generally only been studied at the mean-field level. Here, we extend the renormalized one-loop theory of concentration fluctuations to account for blends of disperse polymers. Analyzing the short and long length-scale fluctuations in a consistent manner, various measures of polymer molecular weight and dispersity arise naturally in the free energy. Thermodynamic analysis in terms of moments of the molecular weight distribution(s) provides exact results for the inverse susceptibility and demonstrates that the theory is not formally renormalizable. However, physically motivated approximations allow for an "effective" renormalization, yielding (1) an effective interaction parameter, χe, which depends directly on the sample dispersities (i.e., Mw/Mn) and leaves the form of the mean-field spinodal unchanged, and (2) an apparent interaction parameter χa that depends on higher-order dispersity indices, for instance Mz/Mw, and characterizes the true limits of blend stability accounting for long-range off-critical fluctuations. We demonstrate the importance of dispersity on several example systems, including both "toy" models that may be realized in computer simulation and more realistic industrially relevant blends. We find that the effects of long-range fluctuations are particularly prominent in blends where the component dispersities are mismatched, especially when there is a small quantity of the high-dispersity species. This can be understood as a consequence of the shift in the critical concentration(s) from the monodisperse value(s). [ABSTRACT FROM AUTHOR]

Polyrotaxanes, which consist of mechanically interlocked bonds with rings threaded onto soft polymer chains, exhibit unique mechanical properties and find applications in diverse fields. In this study, we investigate the anomalous segmental dynamics of supercooled polyrotaxane melts using coarse-grained molecular dynamics simulations. Our simulations reveal that the presence of rings effectively reduces the packing efficiency, resulting in well-contained local motion even below the glass transition temperature. We also observe variations in dynamical free volume, characterized by the Debye–Waller factor, which shows a minimum at a ring coverage of 0.1 on threading chains. Such a non-monotonic dependence on coverage shows great consistency in structural relaxation time and dynamic heterogeneity. Specifically, the high segmental mobility of threading linear chains at large coverage can be attributed to the increased dynamical free volume due to supported rigid rings. However, such anomalous segmental dynamics is limited to length scales smaller than one ring size. Beyond this characteristic length scale, the diffusion is dominated by topological constraints, which significantly reduce the mobility of polyrotaxanes and enhance the dynamic heterogeneity. These findings offer microscopic insights into the unique packing structures and anomalous segmental dynamics of supercooled polyrotaxane melts, facilitating the design of advanced materials based on mechanical interlocking polymers for various applications. [ABSTRACT FROM AUTHOR]

In this work, we determine the dissociation line of the nitrogen (N2) hydrate by computer simulation using the TIP4P/Ice model for water and the TraPPE force field for N2. We use the solubility method proposed recently by some of us to evaluate the dissociation temperature of the hydrate at different pressures, from 500 to 1500 bar. Particularly, we calculate the solubility of N2 in the aqueous solution when it is in contact with a N2-rich liquid phase and when in contact with the hydrate phase via planar interfaces as functions of temperature. Since the solubility of N2 decreases with temperature in the first case and increases with temperature in the second case, both curves intersect at a certain temperature that determines the dissociation temperature at a given pressure. We find a good agreement between the predictions obtained in this work and the experimental data taken from the literature in the range of pressures considered in this work. From our knowledge of the solubility curves of N2 in the aqueous solution, we also determine the driving force for nucleation of the hydrate, as a function of temperature, at different pressures. In particular, we use two different thermodynamic routes to evaluate the change in chemical potential for hydrate formation. Although the driving force for nucleation slightly decreases (in absolute value) when the pressure is increased, our results indicate that the effect of pressure can be considered negligible in the range of pressures studied in this work. To the best of our knowledge, this is the first time the driving force for nucleation of a hydrate that exhibits crystallographic structure sII, along its dissociation line, is studied from computer simulation. [ABSTRACT FROM AUTHOR]

Thermodynamics of far-from-equilibrium systems often require measurement of effective parameters such as temperature. Whether such approach is valid for the general case of resetting protocols, active systems, or of confined systems under time-varying fields is still under investigation. We report on the effect of switching ON-OFF of an asymmetric bistable potential to the mean first passage time (MFPT) of a probed particle to go from one potential minima to the other. Experimental results coupled with numerical simulations shows the potential becoming more symmetric at slow switching. Moreover, the MFPT deviates from equilibrium condition with an effective temperature, Teff < T, at slow switching but approaches room temperature, T, at fast switching. For each switching rate, we quantify how far the system is from equilibrium by measuring deviation from a detailed balance like relation and the net circulation of flux present in phase-space. Both analysis suggest equilibrium condition are met at high switching. [ABSTRACT FROM AUTHOR]

The functionality of many polymeric materials depends on their glass transition temperatures (Tg). In computer simulations, Tg is often calculated from the gradual change in macroscopic properties. Precise determination of this change depends on the fitting protocols. We previously proposed a robust data-driven approach to determine Tg from the molecular dynamics simulation data of a coarse-grained semiflexible polymer model. In contrast to the global macroscopic properties, our method relies on high-resolution microscopic details. Here, we demonstrate the generality of our approach by using various dimensionality reduction and clustering methods and apply it to an atomistic model of acrylic polymers. Our study reveals the explicit contribution of the side chain and backbone residues in influencing the determination of the glass transition temperature. [ABSTRACT FROM AUTHOR]

We propose a generalization of the stochastic resetting mechanism for a Brownian particle diffusing in a one-dimensional periodic potential: randomly in time, the particle gets reset at the bottom of the potential well it was in. Numerical simulations show that in mirror asymmetric potentials, stochastic resetting rectifies the particle's dynamics, with a maximum drift speed for an optimal average resetting time. Accordingly, an unbiased Brownian tracer diffusing on an asymmetric substrate can rectify its motion by adopting an adaptive stop-and-go strategy. Our proposed ratchet mechanism can model the directed autonomous motion of molecular motors and micro-organisms. [ABSTRACT FROM AUTHOR]

Stochastic differential equations (SDE) are a powerful tool to model biological regulatory processes with intrinsic and extrinsic noise. However, numerical simulations of SDE models may be problematic if the values of noise terms are negative and large, which is not realistic for biological systems since the molecular copy numbers or protein concentrations should be non-negative. To address this issue, we propose the composite Patankar-Euler methods to obtain positive simulations of SDE models. A SDE model is separated into three parts, namely, the positive-valued drift terms, negative-valued drift terms, and diffusion terms. We first propose the deterministic Patankar-Euler method to avoid negative solutions generated from the negative-valued drift terms. The stochastic Patankar-Euler method is designed to avoid negative solutions generated from both the negative-valued drift terms and diffusion terms. These Patankar-Euler methods have the strong convergence order of a half. The composite Patankar-Euler methods are the combinations of the explicit Euler method, deterministic Patankar-Euler method, and stochastic Patankar-Euler method. Three SDE system models are used to examine the effectiveness, accuracy, and convergence properties of the composite Patankar-Euler methods. Numerical results suggest that the composite Patankar-Euler methods are effective methods to ensure positive simulations when any appropriate stepsize is used. [ABSTRACT FROM AUTHOR]

Asphaltenes represent a novel class of carbon nanofillers that are of potential interest for many applications, including polymer nanocomposites, solar cells, and domestic heat storage devices. In this work, we developed a realistic coarse-grained Martini model that was refined against the thermodynamic data extracted from atomistic simulations. This allowed us to explore the aggregation behavior of thousands of asphaltene molecules in liquid paraffin on a microsecond time scale. Our computational findings show that native asphaltenes with aliphatic side groups form small clusters that are uniformly distributed in paraffin. The chemical modification of asphaltenes via cutting off their aliphatic periphery changes their aggregation behavior: modified asphaltenes form extended stacks whose size increases with asphaltene concentration. At a certain large concentration (44 mol. %), the stacks of modified asphaltenes partly overlap, leading to the formation of large, disordered super-aggregates. Importantly, the size of such super-aggregates increases with the simulation box due to phase separation in the paraffin–asphaltene system. The mobility of native asphaltenes is systematically lower than that of their modified counterparts since the aliphatic side groups mix with paraffin chains, slowing down the diffusion of native asphaltenes. We also show that diffusion coefficients of asphaltenes are not very sensitive to the system size: enlarging the simulation box results in some increase in diffusion coefficients, with the effect being less pronounced at high asphaltene concentrations. Overall, our findings provide valuable insight into the aggregation behavior of asphaltenes on spatial and time scales that are normally beyond the scales accessible for atomistic simulations. [ABSTRACT FROM AUTHOR]

Forward flux sampling (FFS) is a path sampling technique widely used in computer simulations of crystal nucleation from the melt. In such studies, the order parameter underpinning the progress of the FFS algorithm is often the size of the largest crystalline nucleus. In this work, we investigate the effects of two computational aspects of FFS simulations, using the prototypical Lennard-Jones liquid as our computational test bed. First, we quantify the impact of the positioning of the liquid basin and first interface in the space of the order parameter. In particular, we demonstrate that these choices are key to ensuring the consistency of the FFS results. Second, we focus on the frequently encountered scenario where the population of crystalline nuclei is such that there are multiple clusters of size comparable to the largest one. We demonstrate the contribution of clusters other than the largest cluster to the initial flux; however, we also show that they can be safely ignored for the purposes of converging a full FFS calculation. We also investigate the impact of different clusters merging, a process that appears to be facilitated by substantial spatial correlations—at least at the supercooling considered here. Importantly, all of our results have been obtained as a function of system size, thus contributing to the ongoing discussion on the impact of finite size effects on simulations of crystal nucleation. Overall, this work either provides or justifies several practical guidelines for performing FFS simulations that can also be applied to more complex and/or computationally expensive models. [ABSTRACT FROM AUTHOR]

We explore the relationship between a machine-learned structural quantity (softness) and excess entropy in simulations of supercooled liquids. Excess entropy is known to scale well the dynamical properties of liquids, but this quasi-universal scaling is known to breakdown in supercooled and glassy regimes. Using numerical simulations, we test whether a local form of the excess entropy can lead to predictions similar to those made by softness, such as the strong correlation with particles' tendency to rearrange. In addition, we explore leveraging softness to compute excess entropy in the traditional fashion over softness groupings. Our results show that the excess entropy computed over softness-binned groupings is correlated with activation barriers to rearrangement. [ABSTRACT FROM AUTHOR]

Explicit and implicit size effects in computer simulations result from considering systems with a fixed number of particles and periodic boundary conditions, respectively. We investigate these effects in the relation D*(L) = A(L) exp(α(L)s2(L)) between reduced self-diffusion coefficient D*(L) and two-body excess entropy s2(L) for prototypical simple-liquid systems of linear size L. To this aim, we introduce and validate a finite-size two-body excess entropy integral equation. Our analytical arguments and simulation results show that s2(L) exhibits a linear scaling with 1/L. Since D*(L) displays a similar behavior, we show that the parameters A(L) and α(L) are also linearly proportional to 1/L. By extrapolating to the thermodynamic limit, we report the coefficients A∞ = 0.048 ± 0.001 and α∞ = 1.000 ± 0.013 that agree well with the universal values available in the literature [M. Dzugutov, Nature 381, 137–139 (1996)]. Finally, we find a power law relation between the scaling coefficients for D*(L) and s2(L), suggesting a constant viscosity-to-entropy ratio. [ABSTRACT FROM AUTHOR]

We investigate the effect of pressure on the carbon dioxide (CO2) hydrate–water interfacial free energy along its dissociation line using advanced computer simulation techniques. In previous works, we have determined the interfacial energy of the hydrate at 400 bars using the TIP4P/Ice and TraPPE molecular models for water and CO2, respectively, in combination with two different extensions of the Mold Integration technique [J. Colloid Interface Sci. 623, 354 (2022) and J. Chem. Phys. 157, 134709 (2022)]. Results obtained from computer simulation, 29(2) and 30(2) mJ/m2, are found to be in excellent agreement with the only two measurements that exist in the literature, 28(6) mJ/m2 determined by Uchida et al. [J. Phys. Chem. B 106, 8202 (2002)] and 30(3) mJ/m2 determined by Anderson et al. [J. Phys. Chem. B 107, 3507 (2002)]. Since the experiments do not allow to obtain the variation of the interfacial energy along the dissociation line of the hydrate, we extend our previous studies to quantify the effect of pressure on the interfacial energy at different pressures. Our results suggest that there exists a correlation between the interfacial free energy values and the pressure, i.e., it decreases with the pressure between 100 and 1000 bars. We expect that the combination of reliable molecular models and advanced simulation techniques could help to improve our knowledge of the thermodynamic parameters that control the interfacial free energy of hydrates from a molecular perspective. [ABSTRACT FROM AUTHOR]

Desorption of a self-propelling filament from an attractive surface is studied by computer simulations and the influence of activity, chain length, and chain rigidity is explored. For the flexible filament, we find three scaling regimes of desorption time vs activity with various scaling exponents. At low activity, the scaling law results from the spiral-like detachment kinetics. And at high activity, by theoretical analysis, the desorption is reminiscent of the escaping mechanism of a super-diffusive blob from a potential well at a short time scale. Additionally, the desorption time decreases first and then increases with chain length at low activity, since it is hard to form a spiral for short filaments due to the limited volume repulsion. For high activities, the desorption time approximately scales with chain length, with a scaling exponent ∼ 0.5 , which can be explained by the theory and numerically fitting scaling law between the end-to-end distance of the "globule-like" filament and chain length. Furthermore, a non-monotonic behavior is observed between the desorption time and the chain stiffness. Desorption time slightly decreases first and then rapidly increases with stiffness due to the opposed effects of increasing rigidity on headiing-up time and leaving-away time. In contrast to traditional polymers, the scaling behavior suggests unique desorption characteristics of active polymers. [ABSTRACT FROM AUTHOR]

Self-assembly of chiral particles with an L-shape is explored by Monte-Carlo computer simulations in two spatial dimensions. For sufficiently high packing densities in confinement, a carpet-like texture emerges due to the interlocking of L-shaped particles, resembling a distorted smectic liquid crystalline layer pattern. From the positions of either of the two axes of the particles, two different types of layers can be extracted, which form distinct but complementary entangled networks. These coarse-grained network structures are then analyzed from a topological point of view. We propose a global charge conservation law by using an analogy to uniaxial smectics and show that the individual network topology can be steered by both confinement and particle geometry. Our topological analysis provides a general classification framework for applications to other intertwined dual networks. [ABSTRACT FROM AUTHOR]

In this work, we investigate the physicochemical process of water photolysis to bridge physical and chemical processes by a newly developed first-principles calculation code. The deceleration, thermalization, delocalization, and initial hydration of the extremely low-energy electrons ejected by water photolysis are sequentially tracked in the condensed phase. We show herein the calculated results for these sequential phenomena during 300 fs. Our results indicate that the mechanisms heavily depend on the intermolecular vibration and rotation modes peculiar to water and the momentum transfer between the electrons and the water medium. We suggest that using our results for the delocalized electron distribution will reproduce successive chemical reactions measured by photolysis experiments using a chemical reaction code. We expect our approach to become a powerful technique for various scientific fields related to water photolysis and radiolysis. [ABSTRACT FROM AUTHOR]

We investigate the spatial correlations of microscopic stresses in soft particulate gels using 2D and 3D numerical simulations. We use a recently developed theoretical framework predicting the analytical form of stress–stress correlations in amorphous assemblies of athermal grains that acquire rigidity under an external load. These correlations exhibit a pinch-point singularity in Fourier space. This leads to long-range correlations and strong anisotropy in real space, which are at the origin of force-chains in granular solids. Our analysis of the model particulate gels at low particle volume fractions demonstrates that stress–stress correlations in these soft materials have characteristics very similar to those in granular solids and can be used to identify force chains. We show that the stress–stress correlations can distinguish floppy from rigid gel networks and that the intensity patterns reflect changes in shear moduli and network topology, due to the emergence of rigid structures during solidification. [ABSTRACT FROM AUTHOR]

The measurement of translational diffusion coefficients by nuclear magnetic resonance (NMR) spectroscopy is essential in a broad range of fields, including organic, inorganic, polymer, and supramolecular chemistry. It is also a powerful method for mixture analysis. Spatially encoded diffusion NMR (SPEN DNMR)" is a time efficient technique to collect diffusion NMR data, which is particularly relevant for the analysis of samples that evolve in time. In many cases, motion other than diffusion is present in NMR samples. This is, for example, the case of flow NMR experiments, such as in online reaction monitoring and in the presence of sample convection. Such motion is deleterious for the accuracy of DNMR experiments in general and for SPEN DNMR in particular. Limited theoretical understanding of flow effects in SPEN DNMR experiments is an obstacle for their broader experimental implementation. Here, we present a detailed theoretical analysis of flow effects in SPEN DNMR and of their compensation, throughout the relevant pulse sequences. This analysis is validated by comparison with numerical simulation performed with the Fokker–Planck formalism. We then consider, through numerical simulation, the specific cases of constant, laminar, and convection flow and the accuracy of SPEN DNMR experiments in these contexts. This analysis will be useful for the design and implementation of fast diffusion NMR experiments and for their applications. [ABSTRACT FROM AUTHOR]

A new closure approximation is presented here, and it is based on two thermodynamic relations, namely, a particular case of a local expression together with a global thermodynamic condition. The results obtained from this local approximation are compared with thermodynamic and structural properties determined by using well-established closure approximations as well as numerical simulations for different kinds of interaction potentials. In terms of numerical simulations, the new closure delivers results similar to and sometimes better than the well-known closure relations that are specialized in certain types of interactions. [ABSTRACT FROM AUTHOR]

We report a computer simulation study of the effect of trimethylamine N-oxide (TMAO) on the pressure stability of the hydrophobic contact interaction of two nonpolar α-helices. We found that TMAO counterbalanced the disruptive effect of pressure destabilization on account of an earlier reported electronic polarization effect that led to an increased TMAO dipole moment under compression of the solvent. This direct stabilization mechanism became ineffective when the dipole polarization of TMAO was not considered and was linked to nonspecific van der Waals interactions of TMAO with the nonpolar surfaces of the two helices, which became weaker as TMAO became stronger polarized at high pressure. The corresponding thermodynamic driving forces are discussed and should be generic for hydrophobic interactions under high pressure. The proposed mechanism suggests that TMAO stands out as a piezolyte among stabilizing osmolytes, potentially protecting biological assemblies formed by hydrophobic interactions under extreme pressure conditions. [ABSTRACT FROM AUTHOR]

Adding carbon nanoparticles into organic phase change materials (PCMs) such as paraffin is a common way to enhance their thermal conductivity and to improve the efficiency of heat storage devices. However, the sedimentation stability of such blends can be low due to aggregation of aromatic carbon nanoparticles in the aliphatic paraffin environment. In this paper, we explore whether this important issue can be resolved by the introduction of a polymer agent such as poly(3-hexylthiophene) (P3HT) into the paraffin–nanoparticle blends: P3HT could ensure the compatibility of aromatic carbon nanoparticles with aliphatic paraffin chains. We employed a combination of experimental and computational approaches to determine the impact of P3HT addition on the properties of organic PCMs composed of paraffin and carbon nanoparticles (asphaltenes). Our findings clearly show an increase in the sedimentation stability of paraffin–asphaltene blends, when P3HT is added, through a decrease in average size of asphaltene aggregates as well as in an increase of the blends' viscosity. We also witness the appearance of the yield strength and gel-like behavior of the mixtures. At the same time, the presence of P3HT in the blends has almost no effect on their thermophysical properties. This implies that all properties of the blends, which are critical for heat storage applications, are well preserved. Thus, we demonstrated that adding polyalkylthiophenes to paraffin–asphaltene mixtures led to significant improvement in the performance characteristics of these systems. Therefore, the polymer additives can serve as promising compatibilizers for organic PCMs composed of paraffins and asphaltenes and other types of carbon nanoparticles. [ABSTRACT FROM AUTHOR]

Physical kinetic roughening processes are well-known to exhibit universal scaling of observables that fluctuate in space and time. Are there analogous dynamic scaling laws that are unique to the chemical reaction mechanisms available synthetically and occurring naturally? Here, we formulate an approach to the dynamic scaling of stochastic fluctuations in thermodynamic observables at and away from equilibrium. Both analytical expressions and numerical simulations confirm our dynamic scaling ansatz with associated scaling exponents, function, and law. A survey of common chemical mechanisms reveals classes that organize according to the molecularity of the reactions involved, the nature of the reaction vessel and external reservoirs, (non)equilibrium conditions, and the extent of autocatalysis in the reaction network. Varying experimental parameters, such as temperature, can cause coupled reactions capable of chemical feedback to transition between these classes. While path observables, such as the dynamical activity, have scaling exponents that are time-independent, the variance in the entropy production and flow can have time-dependent scaling exponents and self-averaging properties as a result of temporal correlations that emerge during thermodynamically irreversible processes. Altogether, these results establish dynamic universality classes in the nonequilibrium fluctuations of thermodynamic observables for well-mixed chemical reactions. [ABSTRACT FROM AUTHOR]

Line tension in wetting processes is of high scientific and technological relevance, but its understanding remains vague, mainly because it is difficult to determine. A widely used method to extract line tension relies on the variation of a droplet's contact angle with the droplet's size. Such an approach yields the apparent line tension, which is an effective parameter that factors in numerous contributions to the finite-size dependence, thus masking the actual line tension in terms of the excess free energy of the three-phase contact line. Based on our recent computer simulation study, we investigate how small amounts of nonionic surfactants, such as surface-active impurities, contribute to the apparent line tension in aqueous droplets. When depositing polydisperse droplets, their different surface area-to-volume ratios can result in different final bulk concentrations of surfactants, different excess adsorptions to the interfaces, and, consequently, different contact angles. We show that already trace amounts of longer-chained surfactants in a pre-contaminated liquid are enough to affect measurements of the apparent line tension. Our analysis quantifies to what extent "background" impurities, inevitably present in all kinds of experimental settings, limit the resolution of line tension measurements, which is crucial for avoiding data misinterpretation. [ABSTRACT FROM AUTHOR]

We employ all-atom well-tempered metadynamics simulations to study the mechanistic details of both the early stages of nucleation and crystal decomposition for the benchmark metal–organic framework (MOF) ZIF-8. To do so, we developed and validated a force field that reliably models the modes of coordination bonds via a Morse potential functional form and employs cationic and anionic dummy atoms to capture coordination symmetry. We also explored a set of physically relevant collective variables and carefully selected an appropriate subset for our problem at hand. After a rapid increase of the Zn–N connectivity, we observe the evaporation of small clusters in favor of a few large clusters, which leads to the formation of an amorphous highly connected aggregate. Zn (MIm) 4 2 − and Zn (MIm) 3 − complexes are observed with lifetimes in the order of a few picoseconds, while larger structures, such as four-, five-, and six-membered rings, have substantially longer lifetimes of a few nanoseconds. The free ligands act as "templating agents" for the formation of sodalite cages. ZIF-8 crystal decomposition results in the formation of a vitreous phase. Our findings contribute to a fundamental understanding of MOF's synthesis that paves the way to controlling synthesis products. Furthermore, our developed force field and methodology can be applied to model solution processes that require coordination bond reactivity for other ZIFs besides ZIF-8. [ABSTRACT FROM AUTHOR]

We develop an accurate, highly efficient, and scalable random batch Ewald (RBE) method to conduct molecular dynamics simulations in the isothermal–isobaric ensemble (the NPT ensemble) for charged particles in a periodic box. After discretizing the Langevin equations of motion derived using suitable Lagrangians, the RBE method builds the mini-batch strategy into the Fourier space in the Ewald summation for the pressure and forces such that the computational cost is reduced to O (N) per time step. We implement the method in the Large-scale Atomic/Molecular Massively Parallel Simulator package and report accurate simulation results for both dynamical quantities and statistics for equilibrium for typical systems including all-atom bulk water and a semi-isotropic membrane system. Numerical simulations on massive supercomputing cluster are also performed to show promising central processing unit efficiency of the RBE. [ABSTRACT FROM AUTHOR]

The growth pattern and nucleation rate of carbon dioxide hydrate critically depend on the precise value of the hydrate–water interfacial free energy. There exist in the literature only two independent experimental measurements of this thermodynamic magnitude: one obtained by Uchida et al. [J. Phys. Chem. B 106, 8202 (2002)], 28(6) mJ/m2, and the other by Anderson and co-workers [J. Phys. Chem. B 107, 3507 (2003)], 30(3) mJ/m2. Recently, Algaba et al. [J. Colloid Interface Sci. 623, 354 (2022)] have extended the mold integration method proposed by Espinosa and co-workers [J. Chem. Phys. 141, 134709 (2014)] to deal with the CO2 hydrate–water interfacial free energy (mold integration–guest or MI-H). Computer simulations predict a value of 29(2) mJ/m2, in excellent agreement with experimental data. The method is based on the use of a mold of attractive wells located at the crystallographic positions of the oxygen atoms of water molecules in equilibrium hydrate structures to induce the formation of a thin hydrate slab in the liquid phase at coexistence conditions. We propose here a new implementation of the mold integration technique using a mold of attractive wells located now at the crystallographic positions of the carbon atoms of the CO2 molecules in the equilibrium hydrate structure. We find that the new mold integration–guest methodology, which does not introduce positional or orientational information of the water molecules in the hydrate phase, is able to induce the formation of CO2 hydrates in an efficient way. More importantly, this new version of the method predicts a CO2 hydrate–water interfacial energy value of 30(2) mJ/m2, in excellent agreement with experimental data, which is also fully consistent with the results obtained using the previous methodology. [ABSTRACT FROM AUTHOR]

We investigate the process of the second harmonic generation by plasmonic nano-antennas that exhibit Fano-like resonances. A rigorous fully vectorial Maxwell-hydrodynamics approach is employed to directly calculate the second order susceptibilities as a function of the pump frequency, considering a periodic array of nanodolmens comprised of three Au nanorods. The results of the numerical simulations demonstrate a noticeable enhancement of the second harmonic efficiency by the antisymmetric mode. Additionally, a simple analytical model based on two coupled nonlinear oscillators is proposed. It is shown that the second order optical response can be significantly enhanced at the frequency of the antisymmetric normal mode, thus supporting our numerical results. [ABSTRACT FROM AUTHOR]

Methanol as a basic liquid and the simplest alcohol is widely used in industry and scientific experiments. However, there are still no reliable data on the thermodynamic properties of methanol at high pressure. Here, we present an experimental and computational study of the thermodynamic properties of liquid methanol under high pressure up to 15 kbar, which significantly exceeds previously reported pressures. A temperature response to a small adiabatic change in pressure has been measured using a piston–cylinder apparatus. We have compared our experimental results with the literature data for lower pressures and NIST approximations. We find that all existing experimental data do not agree with each other and with our experiments. The NIST approximations are mainly based on low pressure data and appear to be unreliable in the high pressure region, giving even qualitatively wrong results. OPLS and COMPASS force field models have been used in the method of molecular dynamics. The agreement of molecular simulation with our experimental data is definitely unsatisfactory, which means that the most common computational models of methanol are not sufficiently good. We hope that these experimental data and approximations will help in developing better computational models. [ABSTRACT FROM AUTHOR]

The liquidus temperature curve that characterizes the boundary between the liquid methanol/water mixture and its coexistence with ice Ih is determined using the direct-coexistence method. Several methanol concentrations and pressures of 0.1, 50, and 100 MPa are considered. In this study, we used the TIP4P/Ice model for water and two different models for methanol: OPLS and OPLS/2016, using the geometric rule for the Lennard-Jones cross interactions. We compared our simulation results with available experimental data and found that this combination of models reproduces the liquidus curve for methanol mole fractions reasonably well, up to xm = 0.3 at p = 0.1 MPa. The freezing point depression of these mixtures is calculated and compared to experimental results. We also analyzed the effect of pressure on the liquidus curve and found that both models also reproduce the experimental decrease of the liquidus temperatures as the pressure increases qualitatively well. [ABSTRACT FROM AUTHOR]

While many physical processes are non-equilibrium in nature, the theory and modeling of such phenomena lag behind theoretical treatments of equilibrium systems. The diversity of powerful theoretical tools available to describe equilibrium systems has inspired strategies that map non-equilibrium systems onto equivalent equilibrium analogs so that interrogation with standard statistical mechanical approaches is possible. In this work, we revisit the mapping from the non-equilibrium random sequential addition process onto an equilibrium multi-component mixture via the replica method, allowing for theoretical predictions of non-equilibrium structural quantities. We validate the above approach by comparing the theoretical predictions to numerical simulations of random sequential addition. [ABSTRACT FROM AUTHOR]