arXiv subjects

C. Vega

Publications and source records attributed to C. Vega.

At least 19 recordsLinked to original sources

arXiv2026

Nonlinear Landau Collisions Without Collision Tensors

Far-from-equilibrium plasmas require nonlinear Coulomb collisions, but direct three-dimensional Hermite discretization of the Landau operator needs an impractical dense tensor. By porting quantum chemistry Coulomb-integral methods, we reduce the six-dimensional integrals to one-center Coulomb moments and separable exponential-sum contractions. This gives a four-order-of-magnitude working-memory reduction and enables nonlinear relaxation tests. Numerical simulations preserve invariants and show that finite-basis linearization changes relaxation and produces a fourfold angular error.

physics.plasm-ph↗

arXiv2026

Molecular dynamics study of perchloric acid using the extended Madrid-2019 force field

Perchloric acid (HClO$_4$) is widely used to prepare perchlorate salts with applications in propellants, industry, environmental chemistry, and biology. In this work, we used the intermolecular parameters from the extended Madrid-2019 force field for the perchlorate anion (ClO$_4^-$) and the oxonium cation (H$_3$O$^+$) together with TIP4P/2005 water to model perchloric acid solutions. The force field uses scaled charges of $\pm0.85e$ for monovalent ions and has been widely applied for aqueous ionic systems. We used the model to predict thermodynamic properties [densities and temperatures of maximum in density (TMD)], structural features (ion-water correlations: ion-hydrogen and ion-oxygen), and transport properties (self-diffusion coefficients and viscosity) of perchloric acid solutions at several concentrations. Experimental densities are predicted in excellent agreement up to 10 $m$. We also performed molecular simulations over a wide range of temperatures in order to determine the TMD of perchloric acid at different molalities. Predicted viscosities at 298.15 K and 1 bar are in good agreement with experimental data for concentrations below 4 $m$. Results are discussed in terms of model strengths and limitations.

physics.chem-ph↗

arXiv2025

Scaled charges for ions: an improvement but not the final word for modeling electrolytes in water

In this work we discuss the use of scaled charges when developing force fields for NaCl in water. We shall develop force fields for Na$^+$ and Cl$^-$ using the following values for the scaled charge (in electron units) : 0.75, 0.80, 0.85, 0.92 along with the TIP4P/2005 model of water (for which previous force fields were proposed for q = 0.85 and q = 1). The properties considered in this work are: densities, structural properties, transport properties, surface tension, freezing point depression and maximum in density. All the developed models were able to describe quite well the experimental values of the densities. Structural properties were well described by models with charges equal or larger than 0.85, surface tension by the charge 0.92, maximum in density by the charge 0.85 and transport properties by the charge 0.75. The use of a scaled charge of 0.75 is able to reproduce with high accuracy the viscosities and diffusion coefficients of NaCl solutions by the first time. We have also considered the case of KCl in water and the results obtained were fully consistent with those of NaCl. There is no value of the scaled charge able to reproduce all the properties considered in this work. Although certainly scaled charges are not the final word in the development of force fields for electrolytes in water its use may have some practical advantages. Certain values of the scaled charge could be the best option when the interest is to describe certain experimental properties.

cond-mat.soft↗

arXiv2025

An outlook on the Rapid Decline of Carbon Sequestration in French Forests and associated reporting needs

In this study, we present and discuss changes in carbon storage in the French forests from 1990 to 2022, derived from CITEPA statistics on forest carbon accounting, fed by National Forest Inventory (NFI) data collected through an extensive network of measurement sites across Metropolitan France, and other data sources as regards forest removals. The NFI is designed to provide statistical estimations of growing stock, gains and losses at the national or subnational levels but is unable, in its classical form, to provide detailed spatial outlook, such as on abrupt losses during fires, droughts and insect attacks. A continuing removal of CO2 from the atmosphere by the French forests occurred from 1990 to 2022, because harvest and mortality CO2 losses remained smaller than CO2 removals by forest growth and the increase in forest area (70,000 ha per year but insignificant in terms of increased carbon stocks at present). The CO2 removal by forests was 49.3 MtCO2 yr-1 in 1990, increased to reach a peak of 74.1 MtCO2 yr-1 in 2008 and then quickly decreased down to 37.8 Mton CO2 yr-1 in 2022. After 2017, the sink remained low and mortality rates stayed larger than during any of the previous years. This recent period is marked by climate shocks such as summer droughts and heatwaves in 2015, 2018, 2022, 2023. The full impacts of the droughts in 2022 and 2023 are not yet covered with full precision, as some of the sites measured by the national inventory before those droughts are still pending a second visit. The different regions of France show contrasted trajectories. Southern Mediterranean regions where forests have a low harvest rate have experienced a lower increase in mortality and a sustained CO2 uptake.

physics.ao-ph↗

arXiv2025

Homogeneous nucleation rate of carbon dioxide hydrate formation under experimental condition from Seeding simulations

We investigate the nucleation of carbon dioxide (CO$_2$) hydrates from carbon dioxide aqueous solutions by means of molecular dynamics simulations using the TIP4P/Ice and the TraPPE models for water and CO$_2$ respectively. We work at 400 bar and different temperatures and CO$_2$ concentrations. We use brute force molecular dynamics when the supersaturation or the supercooling are so high so that nucleation occurs spontaneously and Seeding otherwise. We used both methods for a particular state and we get a rate of 10$^{25}\,\text{m}^{-3}\text{s}^{-1}$ for nucleation in a CO$_2$ saturated solution at 255 K (35 K of supercooling). By comparison with our previous work on methane hydrates, we conclude that nucleation of CO$_2$ hydrates is several orders of magnitude faster due to a lower interfacial free energy between the crystal and the solution. By combining our nucleation studies with a recent calculation of the hydrate-solution interfacial free energy at coexistence, we obtain a prediction of the nucleation rate temperature dependence for CO$_{2}$-saturated solutions (the experimentally relevant concentration). On the one hand, we open the window for comparison with experiments for supercooling larger than 25 K. On the other hand, we conclude that homogeneous nucleation is impossible for supercooling lower than 20 K. Therefore, nucleation must be heterogeneous in typical experiments where hydrate formation is observed at low supercooling. To assess the hypothesis that nucleation occurs at the solution-CO$_2$ interface we run spontaneous nucleation simulations in two-phase systems and find, by comparison with single-phase simulations, that the interface does not affect hydrate nucleation, at least at the deep supercooling at which this study was carried out (40 and 45 K). Overall, our work sheds light on molecular and thermodynamic aspects of hydrate nucleation.

cond-mat.soft↗

arXiv2024

Chiral quantum optics: recent developments, and future directions

Chiral quantum optics is a growing field of research where light-matter interactions become asymmetrically dependent on momentum and spin, offering novel control over photonic and electronic degrees of freedom. Recently, the platforms for investigating chiral light-matter interactions have expanded from laser-cooled atoms and quantum dots to various solid-state systems, such as microcavity polaritons and two-dimensional layered materials, integrated into photonic structures like waveguides, cavities, and ring resonators. In this perspective, we begin by establishing the foundation for understanding and engineering these chiral light-matter regimes. We review the cutting-edge platforms that have enabled their successful realization in recent years, focusing on solid-state platforms, and discuss the most relevant experimental challenges to fully harness their potential. Finally, we explore the vast opportunities these chiral light-matter interfaces present, particularly their ability to reveal exotic quantum many-body phenomena, such as chiral many-body superradiance and fractional quantum Hall physics.

physics.optics↗

arXiv2024

Three-phase equilibria of hydrates from computer simulation. I. Finite-size effects in the methane hydrate

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 ($T_3$) 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 $T_3$. 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 $T_3$ 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 the $T_3$ 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.

cond-mat.soft↗

arXiv2024

Three phase equilibria of the methane hydrate in NaCl solutions: A simulation study

Molecular dynamics simulations have been performed to determine the three-phase coexistence temperature for a methane hydrate system in equilibrium with a NaCl solution and a methane gas phase. The direct coexistence technique is used following two approaches, one where the triple coexistence temperature for a given NaCl concentration is narrow down and another where the concentration at a given temperature is equilibrated. In both approaches the results are consistent within the error bars. All simulations were carried out at 400 bar and the range of concentrations explored extends up to a molality of 4 m. TIP4P/2005 for water molecules and a simple Lennard-Jones interaction site for methane were used to simulate the system. Positive deviations from the Lorentz-Berthelot energetic rule have been applied between methane and water (i.e., increasing the attractive interaction between water and methane). Na$^+$ and Cl$^-$ ions were described by using the Madrid-2019 scaled charge model. The role played by finite size effects in the calculation of the coexistence line was analyzed by studying a system with larger number of molecules at a given NaCl concentration. Overall, our simulations show that upon NaCl addition to the liquid water phase, a shift in the three-phase equilibrium line to lower temperatures is produced as occurs in the ice-NaCl(aq) system. The depression of the three-phase coexistence line obtained at different concentrations is in a very good agreement with the experimental results.

physics.chem-ph↗

arXiv2024

In Silico Seawater

Many important processes affecting the Earth's climate are determined by the physical properties of seawater. Desalination of seawater is a significant source of drinking wate.Since the physical properties of seawater governing these processes depend on the molecular interactions among its components, a deeper knowledge of seawater at the molecular level is needed. However MD studies reporting the physical properties of seawater are currently lacking. This is probably due to the usual perception of the seawater composition being too complex to approach.This point of view ignores the fact that physical properties of seawater are dependent on a single parameter representing the composition, namely the salinity. This is because the relative proportions of any two major constituents of seasalt are always the same. An obstacle to performing MD simulations of seawater could have been the unavailability of a satisfactory force field representing the interactions between water molecules and dissolved substances. This drawback has recently been overcome with the proposal of the Madrid-2019 FF.Here we show for the first time that MD simulations of seawater are feasible. We have performed MD simulations of a system, the composition of which is close to the average composition of standard seawater and with the molecular interactions given by the Madrid-2019 force field. We are able to provide quantitative or semiquantitative predictions for a number of relevant physical properties of seawater for temperatures and salinities from the oceanographic range to those relevant to desalination processes. The computed magnitudes include static (density), dynamical (viscosity and diffusion coefficients), structural (ionic hydration, ion-ion distribution functions) and interfacial (surface tension) properties.

physics.chem-ph↗

arXiv2024

A force field of Li$^+$ , Na$^+$ , K$^+$, Mg$^{2+}$, Ca$^{2+}$, Cl$^-$, and SO$_4^{2-}$ in aqueous solution based on the TIP4P/2005 water model and scaled charges for the ions

In this work, a force field for several ions in water is proposed. In particular, we consider the cations Li$^+$ , Na$^+$ , K$^+$, Mg$^{2+}$, Ca$^{2+}$ and the anions Cl$^-$, and SO$_4^{2-}$ . These ions were selected as they appear in the composition of seawater, and they are also found in biological systems. The force field proposed (denoted as Madrid-2019) is nonpolarizable, and both water molecules and sulfate anions are rigid. For water, we use the TIP4P/2005 model. The main idea behind this work is to further explore the possibility of using scaled charges for describing ionic solutions. Monovalent and divalent ions are modeled using charges of 0.85 and 1.7, respectively (in electron units). The model allows a very accurate description of the densities of the solutions up to high concentrations. It also gives good predictions of viscosities up to 3 m concentrations. Calculated structural properties are also in reasonable agreement with the experiment. We have checked that no crystallization occurred in the simulations at concentrations similar to the solubility limit. A test for ternary mixtures shows that the force field provides excellent performance at an affordable computer cost. In summary, the use of scaled charges, which could be regarded as an effective and simple way of accounting for polarization (at least to a certain extend), improves the overall description of ionic systems in water. However, for purely ionic systems, scaled charges will not adequately describe neither the solid nor the melt.

physics.chem-ph↗

arXiv2024

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces , One Property

In this work, we have computed electrical conductivities at ambient conditions of aqueous NaCl and KCl solutions by using the Einstein-Helfand equation. Common force fields (charge q = 1 e) do not reproduce the experimental values of electrical conductivities, viscosities and diffusion coefficients. Recently, we proposed the idea of using different charges to describe the Potential Energy Surface (PES) and the Dipole Moment Surface (DMS). In this work, we implement this concept. The equilibrium trajectories required to evaluate electrical conductivities (within linear response theory) were obtained by using scaled charges (with the value q = 0.75 e ) to describe the PES. The potential parameters were those of the Madrid-Transport force field, which describe accurately viscosities and diffusion coefficients of these ionic solutions. However, integer charges were used to compute the conductivities (thus describing the DMS). The basic idea is that although the scaled charge describes the ion-water interaction better, the integer charge reflects the value of the charge that is transported due to the electric field. The agreement obtained with experiments is excellent, as for the first time electrical conductivities (and the other transport properties) of NaCl and KCl electrolyte solutions are described with high accuracy for the whole concentration range up to their solubility limit. Finally, we propose an easy way to obtain a rough estimate of the actual electrical conductivity of the potential model under consideration using the approximate Nernst-Einstein equation, which neglects correlations between different ions.

physics.chem-ph↗

arXiv2024

The Young-Laplace equation for a solid-liquid interface

The application of the Young-Laplace equation to a solid-liquid interface is considered. Computer simulations show that the pressure inside a solid cluster of hard spheres is smaller than the external pressure of the liquid (both for small and large clusters). That would suggest a negative value for the interfacial free energy. We show that in a Gibbsian description of the thermodynamics of a curved solid-liquid interface in equilibrium, the choice of the thermodynamic (rather than mechanical) pressure is required, as suggested by Tolman for the liquid-gas scenario. With this definition, the interfacial free energy is positive, and the values obtained are in excellent agreement with previous results from nucleation studies. Although for a curved fluid-fluid interface there is no distinction between mechanical and thermal pressures (for a sufficiently large inner phase), in the solid-liquid they do not coincide, as hypothesized by Gibbs.

cond-mat.soft↗

arXiv2022

Minimum in the pressure dependence of the interfacial free energy between ice Ih and water

Despite the importance of ice nucleation, this process has been barely explored at negative pressures. Here, we study homogeneous ice nucleation in stretched water by means of Molecular Dynamics Seeding simulations using the TIP4P/Ice model. We observe that the critical nucleus size, interfacial free energy, free energy barrier, and nucleation rate barely change between isobars from -2600 to 500 bar when they are represented as a function of supercooling. This allows us to identify universal empirical expressions for homogeneous ice nucleation in the pressure range from -2600 to 500 bar. We show that this universal behavior arises from the pressure dependence of the interfacial free energy which we compute by means of the mold integration technique finding a shallow minimum around -2000 bar. Likewise, we show that the change in the interfacial free energy with pressure is proportional to the excess entropy and the slope of the melting line, exhibiting the latter a reentrant behavior also at the same negative pressure. Finally, we estimate the excess energy and the excess entropy of the ice Ih-water interface.

cond-mat.soft↗

arXiv2021

Equivalence between condensation and boiling in a Lennard Jones fluid

Condensation and boiling are phase transitions highly relevant to industry, geology or atmospheric science. These phase transitions are initiated by the nucleation of a drop in a supersaturated vapor and of a bubble in an overstretched liquid respectively. The surface tension between both phases, liquid and vapor, is a key parameter in the development of such nucleation stage. Whereas the surface tension can be readily measured for a flat interface, there are technical and conceptual limitations to obtain it for the curved interface of the nucleus. On the technical side, it is quite difficult to observe a critical nucleus in experiments. From a conceptual point of view, the interfacial free energy depends on the choice of the dividing surface, being the surface of tension the one relevant for nucleation. We bypass the technical limitation by performing simulations of a Lennard Jones fluid where we equilibrate critical nuclei (both drops and bubbles). Regarding the conceptual hurdle, we find the relevant cluster size by searching the radius that correctly predicts nucleation rates and nucleation free energy barriers when combined with Classical Nucleation Theory. With such definition of the cluster size we find the same value of the surface tension for drops and bubbles of a given radius. Thus, condensation and boiling can be viewed as two sides of the same coin. Finally, we combine the data coming from drops and bubbles to obtain, via two different routes, estimates of the Tolman length, a parameter that allows describing the curvature dependence of the surface tension in a theoretical framework.

cond-mat.soft↗

arXiv2014

The mold integration method for the calculation of the crystal-fluid interfacial free energy from simulations

The interfacial free energy between a crystal and a fluid, γ cf, is a highly relevant parameter in phenomena such as wetting or crystal nucleation and growth. Due to the difficulty of measuring γ cf experimentally, computer simulations are often used to study the crystal-fluid interface. Here, we present a novel simulation methodology for the calculation of γ cf . The methodology consists in using a mold composed of potential energy wells to induce the formation of a crystal slab in the fluid at coexistence conditions. This induction is done along a reversible pathway along which the free energy difference between the initial and the final states is obtained by means of thermodynamic integration. The structure of the mold is given by that of the crystal lattice planes, which allows to easily obtain the free energy for different crystal orientations. The method is validated by calculating γ cf for previously studied systems, namely, the hard spheres and the Lennard-Jones systems. Our results for the latter show that the method is accurate enough to deal with the anisotropy of γ cf with respect to the crystal orientation. We also calculate γ cf for a recently proposed continuous version of the hard sphere potential and obtain the same γ cf as for the pure hard sphere system. The method can be implemented both in Monte Carlo and Molecular Dynamics. In fact, we show that it can be easily used in combination with the popular Molecular Dynamics package GROMACS.

cond-mat.stat-mech↗

arXiv2014

Homogeneous ice nucleation evaluated for several water models

In this work, we evaluate by means of computer simulations the rate for ice homogeneous nucleation for several water models such as TIP4P, TIP4P/2005,TIP4P/ICE, and mW (following the same procedure as in Sanz et al. [J. Am. Chem. Soc.135, 15008 (2013)]) in a broad temperature range. We estimate the ice-liquid interfacial free-energy, and conclude that for all water models γ decreases as the temperature decreases. Extrapolating our results to the melting temperature, we obtain a value of the interfacial free-energy between 25 and 32 mN/m in reasonable agreement with the reported experimental values. Moreover, we observe that the values of γ depend on the chosen water model and this is a key factor when numerically evaluating nucleation rates, given that the kinetic prefactor is quite similar for all water models with the exception of the mW (due to the absence of hydrogens). Somewhat surprisingly the estimates of the nucleation rates found in this work for TIP4P/2005 are slightly higher than those of the mW model, even though the former has explicit hydrogens. Our results suggest that it may be possible to observe in computer simulations spontaneous crystallization of TIP4P/2005 at about 60 K below the melting point.

cond-mat.stat-mech↗

arXiv2013

Homogeneous ice nucleation at moderate supercooling from molecular simulation

Among all the freezing transitions, that of water into ice is probably the most relevant to biology, physics, geology or atmospheric science. In this work we investigate homogeneous ice nucleation by means of computer simulations. We evaluate the size of the critical cluster and the nucleation rate for temperatures ranging between 15K and 35K below melting. We use the TIP4P/2005 and the TIP4P/Ice water models. Both give similar results when compared at the same temperature difference with the model's melting temperature. The size of the critical cluster varies from $\sim$8000 molecules (radius$ = 4$nm) at 15K below melting to $\sim$600 molecules (radius$ = 1.7$nm) at 35K below melting. We use Classical Nucleation Theory (CNT) to estimate the ice-water interfacial free energy and the nucleation free energy barrier. We obtain an interfacial free energy of 29(3)mN/m from an extrapolation of our results to the melting temperature. This value is in good agreement both with experimental measurements and with previous estimates from computer simulations of TIP4P-like models. Moreover, we obtain estimates of the nucleation rate from simulations of the critical cluster at the barrier top. The values we get for both models agree within statistical error with experimental measurements. At temperatures higher than 20K below melting we get nucleation rates slower than the appearance of a critical cluster in all the water of the hydrosphere in the age of the universe. Therefore, our simulations predict that water freezing above this temperature must necessarily be heterogeneous.

cond-mat.soft↗

arXiv2012

Free energy calculations for atomic solids through the Einstein crystal/molecule methodology using GROMACS and LAMMPS

In this work the free energy of solid phases is computed for the Lennard-Jones potential and for a model of NaCl. The free energy is evaluated through the Einstein crystal/molecule methodologies using the Molecular Dynamics programs: GROMACS and LAMMPS. The obtained results are compared with the results obtained from Monte Carlo. Good agreement between the different programs and methodologies was found. The procedure to perform the free energy calculations for the solid phase in the Molecular Dynamic programs is described. Since these programs allow to study any continuous intermolecular potential (when given in a tabulated form) this work shows that for isotropic potentials (describing for instance atomic solids or colloidal particles) free energy calculations can be performed on a routinely basis using GROMACS and/or LAMMPS.

cond-mat.soft↗