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The Martini model, a coarse-grained forcefield for biomolecular simulations, has experienced a vast increase in popularity in the past decade. Its building-block approach balances computational efficiency with high chemical specificity, enabling the simulation of organic and inorganic molecules. The modeling of coarse-grained beads as Lennard-Jones particles poses challenges for the accurate reproduction of liquid–vapor interfacial properties, which are crucial in various applications, especially in the case of water. The latest version of the forcefield introduces refined interaction parameters for water beads, tackling the well-known artifact of Martini water freezing at room temperature. In addition, multiple sizes of water beads are available for simulating the solvation of small cavities, including the smallest pockets of proteins. This work focuses on studying the interfacial properties of Martini water, including surface tension and surface thickness. Employing the test-area method, we systematically compute the liquid–vapor surface tension across various combinations of water bead sizes and for temperatures from 300 to 350 K. These findings are of interest to the Martini community as they allow users to account for the low interfacial tension of Martini water by properly adjusting observables computed via coarse-grained simulations to allow for accurate matching against all-atom or experimental results. Surface tension data are also interpreted in terms of local enrichment of the various mixture components at the liquid–vapor interface by means of Gibbs' adsorption formalism. Finally, the critical scaling of the Martini surface tension with temperature is reported to be consistent with the critical exponent of the 3D Ising universality class. [ABSTRACT FROM AUTHOR]

The liquid-to-vapor transition can occur under unexpected conditions in nanopores, opening the door to fundamental questions and new technologies. The physics of boiling in confinement is progressively introduced, starting from classical nucleation theory, passing through nanoscale effects, and terminating with the material and external parameters that affect the boiling conditions. The relevance of boiling in specific nanoconfined systems is discussed, focusing on heterogeneous lyophobic systems, chromatographic columns, and ion channels. The current level of control of boiling in nanopores enabled by microporous materials such as metal organic frameworks and biological nanopores paves the way to thrilling theoretical challenges and to new technological opportunities in the fields of energy, neuromorphic computing, and sensing. [ABSTRACT FROM AUTHOR]

Finite-temperature structures of Cu, Ag, and Au metal nanoclusters are calculated in the entire temperature range from 0 K to melting using a computational methodology that we proposed recently [M. Settem et al., Nanoscale 14, 939 (2022)]. In this method, Harmonic Superposition Approximation (HSA) and Parallel Tempering Molecular Dynamics (PTMD) are combined in a complementary manner. HSA is accurate at low temperatures and fails at higher temperatures. PTMD, on the other hand, effectively samples the high temperature region and melts. This method is used to study the size- and system-dependent competition between various structural motifs of Cu, Ag, and Au nanoclusters in the size range 1–2 nm. Results show that there are mainly three types of structural changes in metal nanoclusters, depending on whether a solid–solid transformation occurs. In the first type, the global minimum is the dominant motif in the entire temperature range. In contrast, when a solid–solid transformation occurs, the global minimum transforms either completely to a different motif or partially, resulting in the co-existence of multiple motifs. Finally, nanocluster structures are analyzed to highlight the system-specific differences across the three metals. [ABSTRACT FROM AUTHOR]

Understanding intrusion and extrusion in nanoporous materials is a challenging multiscale problem of utmost importance for applications ranging from energy storage and dissipation to water desalination and hydrophobic gating in ion channels. Including atomistic details in simulations is required to predict the overall behavior of such systems because the statics and dynamics of these processes depend sensitively on microscopic features of the pore, such as the surface hydrophobicity, geometry, and charge distribution, and on the composition of the liquid. On the other hand, the transitions between the filled (intruded) and empty (extruded) states are rare events that often require long simulation times, which are difficult to achieve with standard atomistic simulations. In this work, we explored the intrusion and extrusion processes using a multiscale approach in which the atomistic details of the system, extracted from molecular dynamics simulations, informed a simple Langevin model of water intrusion/extrusion in the pore. We then used the Langevin simulations to compute the transition times at different pressures, validating our coarse-grained model by comparing it with nonequilibrium molecular dynamics simulations. The proposed approach reproduces experimentally relevant features such as the time and temperature dependence of the intrusion/extrusion cycles, as well as specific details about the shape of the cycle. This approach also drastically increases the timescales that can be simulated, reducing the gap between simulations and experiments and showing promise for more complex systems. [ABSTRACT FROM AUTHOR]

In this work, an extended classical nucleation theory (CNT), including line tension, is used to disentangle classical and non-classical effects in the nucleation of vapor from a liquid confined between two hydrophobic plates at a nanometer distance. The proposed approach allowed us to gauge, from the available simulation work, the importance of elusive nanoscale effects, such as line tension and non-classical modifications of the nucleation mechanism. Surprisingly, the purely macroscopic theory is found to be in quantitative accord with the microscopic data, even for plate distances as small as 2 nm, whereas in extreme confinement (< 1.5 nm), the CNT approximations proved to be unsatisfactory. These results suggest how classical nucleation theory still offers a computationally inexpensive and predictive tool useful in all domains where nanoconfined evaporation occurs—including nanotechnology, surface science, and biology. [ABSTRACT FROM AUTHOR]

Large contact angle hysteresis surfaces were the topic of a contribution in Ref. [19]. They address the relation between vapor of a liquid, a finite contact angle, and a possible wetting transition at saturation vapor pressure. In Ref. [15], the authors apply surfaces with low contact angle hysteresis to the evaporation of drops of salt solutions. Low contact angle hysteresis implies that contact lines or sessile drops move without much resistance. [Extracted from the article]

Heterogeneous nucleation is the preferential means of formation of a new phase. Gas and vapor nucleation in fluids under confinement or at textured surfaces is central for many phenomena of technological relevance, such as bubble release, cavitation, and biological growth. Understanding and developing quantitative models for nucleation is the key to control how bubbles are formed and to exploit them in technological applications. An example is the in silico design of textured surfaces or particles with tailored nucleation properties. However, despite the fact that gas/vapor nucleation has been investigated for more than one century, many aspects still remain unclear and a quantitative theory is still lacking; this is especially true for heterogeneous systems with nanoscale corrugations, for which experiments are difficult. The objective of this focus article is analyzing the main results of the last 10-20 years in the field, selecting few representative works out of this impressive body of the literature, and highlighting the open theoretical questions. We start by introducing classical theories of nucleation in homogeneous and in simple heterogeneous systems and then discuss their extension to complex heterogeneous cases. Then we describe results from recent theories and computer simulations aimed at overcoming the limitations of the simpler theories by considering explicitly the diffuse nature of the interfaces, atomistic, kinetic, and inertial effects. [ABSTRACT FROM AUTHOR]

The string method is a general and flexible strategy to compute the most probable transition path for an activated process (rare event). We apply here the atomistic string method in the density field to the Cassie-Wenzel transition, a central problem in the field of superhydrophobicity. We discuss in detail the mechanism of wetting of a submerged hydrophobic cavity of nanometer size and its dependence on the geometry of the cavity. Furthermore, we analyze the algorithmic analogies between the continuum "interface" string method and CREaM [Giacomello et al., Phys. Rev. Lett. 109, 226102 (2012)], a method inspired by the string that allows for a faster and simpler computation of the mechanism and of the free-energy profiles of the wetting process. [ABSTRACT FROM AUTHOR]

A large number of phenomena of scientific and technological interest involve multiple phases and occur at constant pressure of one of the two phases, e.g., the liquid phase in vapor nucleation. It is therefore of great interest to be able to reproduce such conditions in atomistic simulations. Here we study how popular barostats, originally devised for homogeneous systems, behave when applied straightforwardly to heterogeneous systems. We focus on vapor nucleation from a super-heated Lennard-Jones liquid, studied via hybrid restrained Monte Carlo simulations. The results show a departure from the trends predicted for the case of constant liquid pressure, i.e., from the conditions of classical nucleation theory. Artifacts deriving from standard (global) barostats are shown to depend on the size of the simulation box. In particular, for Lennard-Jones liquid systems of 7000 and 13 500 atoms, at conditions typically found in the literature, we have estimated an error of 10–15 kBT on the free-energy barrier, corresponding to an error of 104–106s−1σ−3 on the nucleation rate. A mechanical (local) barostat is proposed which heals the artifacts for the considered case of vapor nucleation. [ABSTRACT FROM AUTHOR]