Formation of a droplet around a spherical solid particle in supersaturated vapor is considered. The number and stability of equilibrium solutions in a closed small system are studied in the canonical ensemble in comparison to an open system in the grand canonical ensemble. Depending on the system's parameters, two modes exist in the canonical ensemble: the first one with only one solution and the second one with three solutions; the presence of the third solution is due to confinement. The analysis is conducted first on a macroscopic thermodynamic level of description, and then the results are supported by studies within two versions of classical density functional theory: the square-gradient approximation with the Carnahan-Starling equation of state for hard spheres on a completely wettable particle and the random-phase approximation with the fundamental measure theory on a poorly wettable particle. In the latter case, a solution breaking the spherical symmetry is observed at a small total number of molecules.
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http://dx.doi.org/10.1021/acs.langmuir.3c03342 | DOI Listing |
J Chem Inf Model
January 2025
Max-Planck-Institut für Immunbiologie und Epigenetik (MPI-IE), Stübeweg 51, 79108 Freiburg im Breisgau, Germany.
Intrinsically disordered regions are found in most eukaryotic proteins and are enriched with positively and negatively charged residues. While it is often convenient to assume that these residues follow their model-compound p values, recent work has shown that local charge effects (charge regulation) can upshift or downshift side chain p values with major consequences for molecular function. Despite this, charge regulation is rarely considered when investigating disordered regions.
View Article and Find Full Text PDFCurr Biol
December 2024
Department of Pharmacology, Vanderbilt Brain Institute, Vanderbilt Center for Addiction Research, Vanderbilt University, Nashville, TN 37232, USA; Department of Anatomy, Cell Biology, & Physiology, Indiana University School of Medicine, Indianapolis, IN 46202, USA. Electronic address:
Human and non-human primate studies clearly implicate the dorsolateral prefrontal cortex (dlPFC) as critical for advanced cognitive functions. It is thought that intracortical synaptic architectures within the dlPFC are the integral neurobiological substrate that gives rise to these processes. In the prevailing model, each cortical column makes up one fundamental processing unit composed of dense intrinsic connectivity, conceptualized as the "canonical" cortical microcircuit.
View Article and Find Full Text PDFPhys Rev E
November 2024
Dipartimento di Scienze Matematiche, Politecnico di Torino, Corso Duca degli Abruzzi 24, Turin, Italy and INFN, Sezione di Torino, Via P. Giuria 1, 10125 Turin, Italy.
The physical significance of the stochastic processes associated to the generalized Gibbs ensembles is scrutinized here with special attention to the thermodynamic fluctuations of small systems. Differently from the so-called stochastic thermodynamics, which starts from stochastic versions of the first and second law of thermodynamics and associates thermodynamic quantities to microscopic variables, here we consider stochastic variability directly in the macroscopic variables. By recognizing the potential structure of the Gibbs ensembles, when expressed as a function of the potential entropy generation, we obtain exact nonlinear thermodynamic Langevin equations (TLEs) for macroscopic variables, with drift expressed in terms of entropic forces.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095-1569, USA.
Restructuring of surfaces and interfaces plays a key role in the activation and/or deactivation of a wide spectrum of heterogeneous catalysts and functional materials. The statistical ensemble representation can provide unique atomistic insights into this fluxional and metastable realm, but constructing the ensemble is very challenging, especially for the systems with off-stoichiometric reconstruction and varying coverage of mixed adsorbates. Here, we report GOCIA, a versatile global optimizer for exploring the chemical space of these systems.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Dipartimento di Ingegneria, Università degli Studi della Campania "Luigi Vanvitelli," Via Roma 29, 81031 Aversa, Italy.
I studied the ground state properties and phase behavior of a two-dimensional lattice gas in which hard-core particles can have at most one nearest neighboring occupied site on the square lattice. Monte Carlo simulations in the grand-canonical ensemble showed no apparent signature of singular thermodynamic behavior when the chemical potential was increased. The absence of an ordering phase transition is traced to the large number of ground state configurations the model is endowed, which is due to the impossibility of satisfying simultaneously closest packing around a vacancy and around a particle.
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