187 results found
Bresme F, Olarte-Plata JD, Chapman A, et al., 2022, Thermophoresis and thermal orientation of Janus nanoparticles in thermal fields, EUROPEAN PHYSICAL JOURNAL E, Vol: 45, ISSN: 1292-8941
González-Colsa J, Olarte-Plata JD, Bresme F, et al., 2022, Enhanced thermo-optical response by means of anapole excitation., Journal of Physical Chemistry Letters, Vol: 13, Pages: 6230-6235, ISSN: 1948-7185
High refractive index (HRI) dielectric nanostructures offer a versatile platform to control the light-matter interaction at the nanoscale as they can easily support electric and magnetic modes with low losses. An additional property that makes them extraordinary is that they can support low radiative modes, so-called anapole modes. In this work, we propose a spectrally tunable anapole nanoheater based on the use of a dielectric anapole resonator. We show that a gold ring nanostructure, a priori nonresonant, can be turned into a resonant unit by just filling its hole with an HRI material supporting anapole modes, resulting in a more efficient nanoheater able to amplify the photothermal response of the bare nanoring. As proof of concept, we perform a detailed study of the thermoplasmonic response of a gold nanoring used as heating source and a silicon disk, designed to support anapole modes, located in its center acting as an anapolar resonator. Furthermore, we utilize the anapole excitation to easily shift the thermal response of these structures from the shortwave infrared range to the near-infrared range.
Bresme F, Kornyshev AA, Perkin S, et al., 2022, Electrotunable friction with ionic liquid lubricants, NATURE MATERIALS, ISSN: 1476-1122
Chapman A, Bresme F, 2022, Polarisation of water under thermal fields: the effect of the molecular dipole and quadrupole moments., Physical Chemistry Chemical Physics, Vol: 24, Pages: 14924-14936, ISSN: 1463-9076
The investigation of the behaviour of water under thermal fields is important to understand thermoelectricity of solutions, aqueous suspensions, bioelectric effects or the properties of wet materials under spatially inhomogeneous temperature conditions. Here we discuss the response of bulk water to external thermal fields using non-equilibrium molecular dynamics simulations, and five widely used forcefields: TIP4P/2005, TIP4P/2005f, OPC, SPC/E and TIP3P. These models all show the thermal polarisation (TP) effect in bulk water, namely the build-up of an electrostatic field induced by the temperature gradient. The strength of this effect is ∼0.1-1 mV K-1 at near-standard conditions for all forcefields, supporting the generality of TP. Moreover, all the models predict a temperature inversion of the polarisation field, although the inversion temperatures vary significantly across different models. We rationalise this result by deriving theoretical equations that describe the temperature inversion as a balance of the isobaric thermal expansion, dipole orientation in the thermal field and the ratio of the molecular dipole/quadrupole moments. Lower ratios lead to higher inversion temperatures. Based on our results, we conclude that the accuracy of the forcefields describing the TP effect decreases as, TIP4P/2005 ∼ TIP4P/2005f ∼ OPC > SPC/E > TIP3P. At coexistence conditions, the inversion temperature is expected to be around 400 K. Furthermore, we establish a correlation between the TP inversion temperature and the temperature corresponding to the minimum of the liquid-vapour surface potential of water.
Olarte-Plata JD, Bresme F, 2022, Thermal conductance of the water-gold interface: the impact of the treatment of surface polarization in non-equilibrium molecular simulations., Journal of Chemical Physics, Vol: 156, Pages: 204701-204701, ISSN: 0021-9606
Interfacial thermal conductance (ITC) quantifies heat transport across material-fluid interfaces. It is a property of crucial importance to study heat transfer processes at both macro- and nanoscales. Therefore, it is essential to accurately model the specific interactions between solids and liquids. Here, we investigate the thermal conductance of gold-water interfaces using polarizable and non-polarizable models. Both models have been fitted to reproduce the interfacial tension of the gold-water interface, but they predict significantly different ITCs. We demonstrate that the treatment of polarization using Drude-like models, widely employed in molecular simulations, leads to a coupling of the solid and liquid vibrational modes that give rise to a significant overestimation of the ITCs. We analyze the dependence of the vibrational coupling with the mass of the Drude particle and propose a solution to the artificial enhancement of the ITC, preserving at the same time the polarization response of the solid. Based on our calculations, we estimate ITCs of 200 MW/(m2 K) for the water-gold interface. This magnitude is comparable to that reported recently for gold-water interfaces [279 ± 16 MW/(m2 K)] using atomic fluctuating charges to account for the polarization contribution.
Hernández-Muñoz J, Bresme F, Tarazona P, et al., 2022, Bending modulus of lipid membranes from density correlation functions., Journal of Chemical Theory and Computation, Vol: 18, Pages: 3151-3163, ISSN: 1549-9618
The bending modulus κ quantifies the elasticity of biological membranes in terms of the free energy cost of increasing the membrane corrugation. Molecular dynamics (MD) simulations provide a powerful approach to quantify κ by analyzing the thermal fluctuations of the lipid bilayer. However, existing methods require the identification and filtering of non-mesoscopic fluctuation modes. State of the art methods rely on identifying a smooth surface to describe the membrane shape. These methods introduce uncertainties in calculating κ since they rely on different criteria to select the relevant fluctuation modes. Here, we present a method to compute κ using molecular simulations. Our approach circumvents the need to define a mesoscopic surface or an orientation field for the lipid tails explicitly. The bending and tilt moduli can be extracted from the analysis of the density correlation function (DCF). The method introduced here builds on the Bedeaux and Weeks (BW) theory for the DCF of fluctuating interfaces and on the coupled undulatory (CU) mode introduced by us in previous work. We test the BW-DCF method by computing the elastic properties of lipid membranes with different system sizes (from 500 to 6000 lipid molecules) and using coarse-grained (for POPC and DPPC lipids) and fully atomistic models (for DPPC). Further, we quantify the impact of cholesterol on the bending modulus of DPPC bilayers. We compare our results with bending moduli obtained with X-ray diffraction data and different computer simulation methods.
Jiang M, Olarte-Plata JD, Bresme F, 2022, Heterogeneous thermal conductance of nanoparticle-fluid interfaces: An atomistic nodal approach, Journal of Chemical Physics, Vol: 156, ISSN: 0021-9606
The Interfacial Thermal Conductance (ITC) is a fundamental property of materials and has particular relevance at the nanoscale. The ITC quantifies the thermal resistance between materials of different compositions or between fluids in contact with materials. Furthermore, the ITC determines the rate of cooling/heating of the materials and the temperature drop across the interface. Here, we propose a method to compute local ITCs and temperature drops of nanoparticle–fluid interfaces. Our approach resolves the ITC at the atomic level using the atomic coordinates of the nanomaterial as nodes to compute local thermal transport properties. We obtain high-resolution descriptions of the interfacial thermal transport by combining the atomistic nodal approach, computational geometry techniques, and “computational farming” using non-equilibrium molecular dynamics simulations. We use our method to investigate the ITC of nanoparticle–fluid interfaces as a function of the nanoparticle size and geometry, targeting experimentally relevant structures of gold nanoparticles: capped octagonal rods, cuboctahedrons, decahedrons, rhombic dodecahedrons, cubes, icosahedrons, truncated octahedrons, octahedrons, and spheres. We show that the ITC of these very different geometries varies significantly in different regions of the nanoparticle, increasing generally in the order face < edge < vertex. We show that the ITC of these complex geometries can be accurately described in terms of the local coordination number of the atoms in the nanoparticle surface. Nanoparticle geometries with lower surface coordination numbers feature higher ITCs, and the ITC generally increases with the decreasing particle size
Gonzalez-Colsa J, Serrera G, Maria Saiz J, et al., 2022, Gold nanodoughnut as an outstanding nanoheater for photothermal applications, Optics Express, Vol: 30, Pages: 125-137, ISSN: 1094-4087
Photoinduced hyperthermia is a cancer therapy technique that induces death to cancerous cells via heat generated by plasmonic nanoparticles. While previous studies have shown that some nanoparticles can be effective at killing cancer cells under certain conditions, there is still a necessity (or the need) to improve its heating efficiency. In this work, we perform a detailed theoretical study comparing the thermoplasmonic response of the most effective nanoparticle geometries up to now with a doughnut-shaped nanoparticle. We numerically demonstrate that the latter exhibits a superior tunable photothermal response in practical illumination conditions (unpolarized light). Furthermore, we show that nanoparticle heating in fluidic environments, i.e., nanoparticles undergoing Brownian rotations, strongly depends on the particle orientation with respect to the illumination source. We conclude that nanodoughnuts are the best nanoheaters in our set of structures, with an average temperature increment 40% higher than the second best nanoheater (nanodisk). Furthermore, nanodoughnuts feature a weak dependence on orientation, being therefore ideal candidates for photothermal therapy applications. Finally, we present a designing guide, covering a wide range of toroid designs, which can help on its experimental implementation.
Olarte-Plata JD, Bresme F, 2022, The impact of the thermostats on the non-equilibrium computer simulations of the interfacial thermal conductance, Molecular Simulation, Vol: 48, Pages: 87-98, ISSN: 0892-7022
Non-equilibrium molecular dynamics simulations have expanded our ability to investigate interfacial thermal transport and quantify the interfacial thermal conductance (ITC) across solid and fluid interfaces. NEMD studies have highlighted the importance of interfacial degrees of freedom and the need to include effects beyond traditional theoretical methods that rely on bulk properties. NEMD simulations often use explicit hot and cold thermostats to set up thermal gradients. We analyse here the impact of the thermostat on the calculated ITC of the gold-water interface. We employ a polarisable model for gold based on Drude oscillators. We show that the ‘local’ Langevin thermostat modifies the vibrational density of states of the polarisable solid, resulting in ITCs that depend very strongly on the damping constant of the thermostat. We report an increase of the ITC of up to 40% for short damping times. Damping times longer than the characteristic heat flux relaxation time of the solid lead to converging ITCs. In contrast, the ITCs obtained with global canonical velocity rescale thermostats are independent of the damping time but lead to a break of equipartition for Drude particles. Setting individual thermostats for the core and shell sites in the Drude particle solves this problem.
Olarte-Plata JD, Gabriel J, Albella P, et al., 2021, Spatial control of heat flow at the nanoscale using Janus Particles., ACS Nano, Vol: 16
Janus nanoparticles (JNPs) feature heterogeneous compositions, bringing opportunities in technological and medical applications. We introduce a theoretical approach based on nonequilibrium molecular dynamics simulations and heat transfer continuum theory to investigate the temperature fields generated around heated spherical JNPs covering a wide range of particle sizes, from a few nm to 100 nm. We assess the performance of these nanoparticles to generate anisotropic heating at the nanoscale. We demonstrate that the contrasting interfacial thermal conductances of the fluid-material interfaces arising from the heterogeneous composition of the JNPs can be exploited to control the thermal fields around the nanoparticle, leading to a temperature difference between both sides of the nanoparticle (temperature contrast) that is significant for particles comprising regions with disparate hydrophilicity. We illustrate this idea using coarse-grained and atomistic models of gold nanoparticles with hydrophobic and hydrophilic coatings, in water. Furthermore, we introduce a continuum model to predict the temperature contrast as a function of the interfacial thermal conductance and nanoparticle size. We further show that, unlike homogeneous nanoparticles, the interfacial fluid temperature depends on the interfacial thermal conductance of Janus nanoparticles.
Gittus OR, Bresme F, 2021, Thermophysical properties of water using reactive force fields., Journal of Chemical Physics, Vol: 155, Pages: 1-28, ISSN: 0021-9606
The widescale importance and rich phenomenology of water continue to motivate the development of computational models. ReaxFF force fields incorporate many characteristics desirable for modeling aqueous systems: molecular flexibility, polarization, and chemical reactivity (bond formation and breaking). However, their ability to model the general properties of water has not been evaluated in detail. We present comprehensive benchmarks of the thermophysical properties of water for two ReaxFF models, the water-2017 and CHON-2017_weak force fields. These include structural, electrostatic, vibrational, thermodynamic, coexistence, and transport properties at ambient conditions (300 K and 0.997 g cm-3) and along the standard pressure (1 bar) isobar. Overall, CHON-2017_weak predicts more accurate thermophysical properties than the water-2017 force field. Based on our results, we recommend potential avenues for improvement: the dipole moment to quadrupole moment ratio, the self-diffusion coefficient, especially for water-2017, and the gas phase vibrational frequencies with the aim to improve the vibrational properties of liquid water.
Di Lecce S, Kornyshev AA, Urbakh M, et al., 2021, Structural effects in nanotribology of nanoscale films of ionic liquids confined between metallic surfaces, Physical Chemistry Chemical Physics, Vol: 23, Pages: 22174-22183, ISSN: 1463-9076
Room Temperature Ionic Liquids (RTILs) attract significant interest in nanotribology. However, their microscopic lubrication mechanism is still under debate. Here, using non-equilibrium molecular dynamics simulations, we investigate the lubrication performance of ultra-thin (<2 nm) films of [C2MIM]+ [NTf2]− confined between plane-parallel neutral surfaces of Au(111) or Au(100). We find that films consisting of tri-layers or bilayers, form ordered structures with a flat orientation of the imidazolium rings with respect to the gold surface plane. Tri-layers are unstable against loads >0.5 GPa, while bi-layers sustain pressures in the 1–2 GPa range. The compression of these films results in monolayers that can sustain loads of several GPa without significant loss in their lubrication performance. Surprisingly, in such ultra-thin films the imidazolium rings show higher orientational in-plane disorder, with and the rings adopting a tilted orientation with respect to the gold surface. The friction force and friction coefficient of the monolayers depends strongly on the structure of the gold plates, with the friction coefficient being four times higher for monolayers confined between Au(100) surfaces than for more compact Au(111) surfaces. We show that the general behaviour described here is independent of whether the metallic surfaces are modelled as polarizable or non-polarizable surfaces and speculate on the nature of this unexpected conclusion.
Haimov E, Chapman A, Bresme F, et al., 2021, Theoretical demonstration of a capacitive rotor for generation of alternating current from mechanical motion, Nature Communications, Vol: 12, Pages: 3678-3678, ISSN: 2041-1723
Innovative concepts and materials are enabling energy harvesters for slower motion, particularly for personal wearables or portable small-scale applications, hence contributing to a future sustainable economy. Here we propose a principle for a capacitive rotor device and analyze its operation. This device is based on a rotor containing many capacitors in parallel. The rotation of the rotor causes periodic capacitance changes and, when connected to a reservoir-of-charge capacitor, induces alternating current. The properties of this device depend on the lubricating liquid situated between the capacitor’s electrodes, be it a highly polar liquid, organic electrolyte, or ionic liquid – we consider all these scenarios. An advantage of the capacitive rotor is its scalability. Such a lightweight device, weighing tens of grams, can be implemented in a shoe sole, generating a significant power output of the order of Watts. Scaled up, such systems can be used in portable wind or water turbines.
Monet G, Berthoumieux H, Bresme F, et al., 2021, Nonlocal Dielectric Response of Water in Nanoconfinement, PHYSICAL REVIEW LETTERS, Vol: 126, ISSN: 0031-9007
Font F, Micou W, Bresme F, 2021, Non-equilibrium molecular dynamics and continuum modelling of transient freezing of atomistic solids, International Journal of Heat and Mass Transfer, Vol: 164, Pages: 1-11, ISSN: 0017-9310
In this work we investigate the transient solidification of a Lennard-Jones liquid using non-equilibrium molecular dynamics simulations and continuum heat transfer theory. The simulations are performed in slab-shaped boxes, where a cold thermostat placed at the centre of the box drives the solidification of the liquid. Two well-defined solid fronts propagate outwards from the centre towards the ends of the box until solidification is completed. A continuum phase change model that accounts for the difference between the solid and the liquid densities is formulated to describe the evolution of the temperature and the position of the solidification front. Simulation results for a small and a large nanoscale system, of sizes 30.27 nm and 60.54 nm, are compared with the predictions of the theoretical model. Following a transient period of ~ 20-40 ps and a displacement of the solidification front of 1-2.5 nm we find that the simulations and the continuum theory show good agreement. We use this fact to combine the simulation and theoretical approaches to design a simple procedure to calculate the latent heat associated to the liquid-solid phase transition. We also perform simulations of the homogeneous freezing process, i.e. in the absence of a temperature gradient and at constant temperature, by quenching the liquid at supercooled temperatures. We demonstrate that, for comparable temperature conditions, the solidification rate of homogenous freezing is much faster than the one obtained under a thermal gradient. Our study and conclusions should be of general interest to a wide range of atomistic solids.
Galteland O, Bresme F, Hafskjold B, 2020, Solvent-mediated forces between ellipsoidal nanoparticles adsorbed at liquid-vapor interfaces., Langmuir: the ACS journal of surfaces and colloids, Vol: 36, Pages: 14530-14538, ISSN: 0743-7463
Classical capillary theory predicts that a non-neutrally wetting ellipsoidal particle adsorbed at a liquid-vapor interface will deform the interface. The deformation gives rise to anisotropic capillary forces of a quadrupolar nature that induce strong directionality in the particle interactions. Here, we investigate the interactions between nanoparticles with characteristic lengths of 1-5 nm. We show that the near-field interactions are dominated by solvent-mediated forces, which arise from the fluid packing between the nanoparticles and direct nanoparticle-nanoparticle interactions. The solvent-mediated forces are two orders of magnitude larger than the estimated capillary force. We find that interacting ellipsoidal nanoparticles adsorbed at the liquid-vapor interface have a larger repulsion in the depletion region than the nanoparticles submerged in a dense bulk phase and argue that this is because of a negative line tension associated with the three-phase line.
Pivnic K, Bresme F, Kornyshev AA, et al., 2020, Electrotunable friction in diluted room temperature ionic liquids: implications for nanotribology, ACS Applied Nano Material, Vol: 3, Pages: 10708-10719, ISSN: 2574-0970
Using nonequilibrium molecular dynamics (NEMD) simulations, we study the mechanism of electrotunable friction in the mixture of a room temperature ionic liquid (RTIL), BMIM PF6, and an organic solvent, acetonitrile. The dilution itself helps to reduce the viscosity and thereby reduce the viscous contribution to friction. At the same time, we find that under nanoscale confinement conditions, diluted RTIL solutions, of just ∼10% molar fraction, still feature a remarkable variation of the friction force with the electrode surface charge density, not weaker than had been earlier shown for nanoconfined pure RTILs. In both classes of systems the electrotunable friction response is due to accumulation of counterions at charged surfaces. For both diluted mixtures and pure RTILs, the friction force is minimal for uncharged surfaces and it increases with surface charge of either sign but only in the range of low and moderate surface charges (16–32 μC/cm2). At higher surface charges (43–55 μC/cm2), the effect is different: in the pure RTIL, the friction force continues to increase with the surface charge, while in the diluted RTIL mixture it features a maximum, with a reduction of friction with the increasing surface charge. This contrasting behavior is explained by the difference in the slip conditions found for the pure and the diluted RTIL solutions in contact with highly charged surfaces. Overall, we demonstrate that nanoscale films of diluted mixtures of RTIL provide lower friction forces than the pure RTIL films, preserving at the same time a significant electrotunable response when the liquids are confined between symmetrically charged surfaces. Nanoconfinement between asymmetrically charged surfaces leads to a reduction of friction compared to the symmetric case, with a concomitant decrease in the range of friction variation with the surface charge density. Our results highlight the potential of diluted RTIL mixtures as cost-effective electrotunab
Gittus OR, Albella P, Bresme F, 2020, Polarization of acetonitrile under thermal fields via non-equilibrium molecular dynamics simulations., Journal of Chemical Physics, Vol: 153, Pages: 204503-204503, ISSN: 0021-9606
We show that thermal gradients polarize liquid and supercritical acetonitrile. The polarization results in a stationary electrostatic potential that builds up between hot and cold regions. The strength of the field increases with the static dielectric constant or with decreasing temperature. At near standard conditions, the thermal polarization coefficient is ∼-0.6 mV/K, making it possible to induce significant electrostatic fields, ∼103 V/m, with thermal gradients ∼1 K/μm. At supercritical conditions, ∼600 K and 0.249 g/cm3 (the critical isochore), the electrostatic field is of the same order, despite the low dielectric constant of the fluid. In this case, the electrostatic field is determined by the enhanced rotational diffusion of the molecules and stronger cross-coupling between heat and polarization fluxes. We show that the coupling between the heat and polarization fluxes influences the thermal conductivity of acetonitrile, which becomes a worse heat conductor. For the thermodynamic states investigated in this work, the thermal polarization effect leads to a ∼2%-5% reduction in thermal conductivity.
Di Lecce S, Albrecht T, Bresme F, 2020, Taming the thermodiffusion of alkali halide solutions in silica nanopores, Nanoscale, Vol: 12, Pages: 23626-23635, ISSN: 2040-3364
Thermal fields give rise to thermal coupling phenomena, such as mass and charge fluxes, which are useful in energy recovery applications and nanofluidic devices for pumping, mixing or desalination. Here we use state of the art non-equilibrium molecular simulations to quantify the thermodiffusion of alkali halide solutions, LiCl and NaCl, confined in silica nanopores, targeting diameters of the order of those found in mesoporous silica nanostructures. We show that nanoconfinement modifies the thermodiffusion behaviour of the solution. Under confinement conditions, the solutions become more thermophilic, with a preference to accumulate at hot sources, or thermoneutral, with the thermodiffusion being inhibited. Our work highlights the importance of nanoconfinement in thermodiffusion and outlines strategies to tune mass transport at the nanoscale, using thermal fields.
Di Lecce S, Kornyshev AA, Urbakh M, et al., 2020, Lateral ordering in nanoscale ionic liquid films between charged surfaces enhances lubricity., ACS Nano, Vol: 14, Pages: 13256-13267, ISSN: 1936-0851
Electric fields modify the structural and dynamical properties of room temperature ionic liquids (RTILs) providing a physical principle to develop tunable lubrication devices. Using nonequilibrium molecular dynamics atomistic simulations, we investigate the impact of the composition of imidazolium RTILs on the in-plane ordering of ionic layers in nanogaps. We consider imidazolium cations and widely used anions featuring different molecular structures, spherical ([BF4]-), elongated surfactant-like ([C2SO4]-), and elongated with a more delocalized charge ([NTf2]-). The interplay of surface charge, surface polarity, and anion geometry enables the formation of crystal-like structures in [BF4]- and [NTf2]- nanofilms, while [C2SO4]- nanofilms form disordered layers. We study how the ordering of the ionic liquid lubricant in the nanogap affects friction. Counterintuitively, we find that the friction force decreases with the ability of the RTILs to form crystal-like structures in the confined region. The crystallization can be activated or inhibited by changing the polarity of the surface, providing a mechanism to tune friction with electric fields.
Carter JW, Gonzalez MA, Brooks NJ, et al., 2020, Flip-flop asymmetry of cholesterol in model membranes induced by thermal gradients, Soft Matter, Vol: 16, Pages: 5925-5932, ISSN: 1744-683X
Lipid asymmetry is a crucial property of biological membranes and significantly influences their physical and mechanical properties. It is responsible for maintaining different chemical environments on the external and internal surfaces of cells and organelles and plays a vital role in many biological processes such as cell signalling and budding. In this work we show, using non-equilibrium molecular dynamics (NEMD) simulations, that thermal fields can induce lipid asymmetry in biological membranes. We focus our investigation on cholesterol, an abundant lipid in the plasma membrane, with a rapid flip-flop rate, significantly influencing membrane properties. We demonstrate that thermal fields induce membrane asymmetry with cholesterol showing thermophobic behaviour and therefore accumulating on the cold side of the membrane. This work highlights a possible experimental route to preparing and controlling asymmetry in synthetic membranes.
Gonzalez MA, Bresme F, 2020, Membrane-ion interactions modify the lipid flip-flop dynamics of biological membranes: a molecular dynamics study, The Journal of Physical Chemistry B: Biophysical Chemistry, Biomaterials, Liquids, and Soft Matter, Vol: 124, Pages: 5156-5162, ISSN: 1520-5207
The asymmetric distribution of lipids in the cell membrane is maintained by protein transporters, and in the absence of proteins, by spontaneous flip-flop of lipids that involve the formation of transient pores in the membrane. The composition of the cell membranes influences the metabolism of the cell by modulating the function of transmembrane proteins, and flip-flop processes are therefore of key importance. Membranes are in direct contact with aqueous solutions, containing ions of different compositions that interact with the lipid head groups or cross the cell membrane through transmembrane channels. The impact of the ions on the lipid flip-flop rates is, however, an outstanding question. Here, we show that the flip-flop rate slows down significantly with the increasing valence of the cation, from minutes for monovalent cations (Na+, K+) to hours for divalent (Mg2+, Ca2+) or days for trivalent cations (Yb3+).
Zheng L, Rucker M, Bultreys T, et al., 2020, Surrogate models for studying the wettability of nanoscale natural rough surfaces using molecular dynamics, Energies, Vol: 13, ISSN: 1996-1073
A molecular modeling methodology is presented to analyze the wetting behavior of natural surfaces exhibiting roughness at the nanoscale. Using atomic force microscopy, the surface topology of a Ketton carbonate is measured with a nanometer resolution, and a mapped model is constructed with the aid of coarse-grained beads. A surrogate model is presented in which surfaces are represented by two-dimensional sinusoidal functions defined by both an amplitude and a wavelength. The wetting of the reconstructed surface by a fluid, obtained through equilibrium molecular dynamics simulations, is compared to that observed by the different realizations of the surrogate model. A least-squares fitting method is implemented to identify the apparent static contact angle, and the droplet curvature, relative to the effective plane of the solid surface. The apparent contact angle and curvature of the droplet are then used as wetting metrics. The nanoscale contact angle is seen to vary significantly with the surface roughness. In the particular case studied, a variation of over 65° is observed between the contact angle on a flat surface and on a highly spiked (Cassie–Baxter) limit. This work proposes a strategy for systematically studying the influence of nanoscale topography and, eventually, chemical heterogeneity on the wettability of surfaces.
Olarte-Plata JD, Brekke-Svaland G, Bresme F, 2020, The influence of surface roughness on the adhesive interactions and phase behavior of suspensions of calcite nanoparticles, Publisher: ROYAL SOC CHEMISTRY
Olarte-Plata JD, Bresme F, 2020, Orientation of Janus particles under thermal fields: The role of internal mass anisotropy., Journal of Chemical Physics, Vol: 152, Pages: 204902-204902, ISSN: 0021-9606
Janus particles (JPs) are a special kind of colloids that incorporate two hemispheres with distinct physical properties. These particles feature a complex phase behavior, and they can be propelled with light by heating them anisotropically when one of the hemispheres is metallic. It has been shown that JPs can be oriented by a homogeneous thermal field. We show using multiscale simulations and theory that the internal mass gradient of the JPs can enhance and even reverse the relative orientation of the particle with the thermal field. This effect is due to a coupling of the internal anisotropy of the particle with the heat flux. Our results help rationalize previous experimental observations and open a route to control the behavior of JPs by exploiting the synergy of particle-fluid interactions and particle internal mass composition.
Olarte-Plata JD, Brekke-Svaland G, Bresme F, 2020, The influence of surface roughness on the adhesive interactions and phase behavior of suspensions of calcite nanoparticles., Nanoscale, Vol: 12, Pages: 11165-11173, ISSN: 2040-3364
We investigate the impact of nanoparticle roughness on the phase behaviour of suspensions in models of calcium carbonate nanoparticles. We use a Derjaguin approach that incorporates roughness effects and interactions between the nanoparticles modelled with a combination of DLVO forces and hydration forces, derived using experimental data and atomistic molecular dynamics simulations, respectively. Roughness effects, such as atomic steps or terraces appearing in mineral surfaces result in very different effective inter-nanoparticle potentials. Using stochastic Langevin Dynamics computer simulations and the effective interparticle interactions we demonstrate that relatively small changes in the roughness of the particles modify significantly the stability of the suspensions. We propose that the sensitivity of the phase behavior to the roughness is connected to the short length scale of the adhesive attraction arising from the ordering of water layers confined between calcite surfaces. Particles with smooth surfaces feature strong adhesive forces, and form gel fractal structures, while small surface roughness, of the order of atomic steps in mineral faces, stabilize the suspension. We believe that our work helps to rationalize the contrasting experimental results that have been obtained recently using nanoparticles or extended surfaces, which provide support for the existence of adhesive or repulsive interactions, respectively. We further use our model to analyze the synergistic effects of roughness, pH and ion concentration on the phase behavior of suspensions, connecting with recent experiments using calcium carbonate nanoparticles.
Tascini AS, Wang S, Seddon JM, et al., 2020, Fats’ love–hate relationships: a molecular dynamics simulation and hands-on experiment outreach activity to introduce the amphiphilic nature and biological functions of lipids to young students and the general public, Journal of Chemical Education, Vol: 97, Pages: 1360-1367, ISSN: 0021-9584
Lipids are fundamental components of biological organisms and have important applications in the pharmaceutical, food, and cosmetics industries. Thus, it is important that young students and the general public properly understand the basic properties of lipids and how these relate to their biological and industrial roles. Here, we use molecular dynamics computer simulations and a simple, safe, and inexpensive popular hands-on activity, to communicate to participants why and how lipid molecules play a fundamental role in all living organisms and in our bodies. The activity is called “Fats’ Love–Hate Relationships”, to highlight how the different parts of amphiphilic lipids interact with water. This “love–hate relationship” is vital to the biological functions of lipids and drives the formation of lipid structures that can be visualized at molecular scale with the computer simulations. The participants were encouraged to investigate the interactions between milk lipids and soap surfactants, creating beautiful complex artwork that they could then take home. The hands-on activity was accompanied by a video of a molecular simulation that illustrates milk–soap interactions at a molecular scale and helps to explain how the amphiphilicity of lipids creates the beautiful artwork at a molecular level. The outreach activity has been performed in science festivals and in classrooms and has been well received by participants of all ages with multiple learner comprehension levels (primary and secondary school students and the general public). By combining molecular simulation, explanations of the amphiphilic structure of the lipids, and an engaging hands-on activity, we explained how lipids interact with water and surfactants and inspired discussions on the link between the structure of the lipids and their biological function, namely, their structural and protective roles as a key component of cell membranes.
Muller E, Trusler J, Bresme F, et al., 2020, Employing SAFT coarse grained force fields for the molecular simulation of thermophysical and transport properties of CO2 – n-alkane mixtures, Journal of Chemical and Engineering Data, Vol: 65, Pages: 1159-1171, ISSN: 0021-9568
We report an assessment of the predictive and correlative capability of the SAFT coarse-grained force field as applied to mixtures of CO2 with n-decane and n-hexadecane. We obtain the pure and cross-interaction parameters by matching simulations to experimental phase equilibrium behavior and transfer these parameters to predict shear viscosities. We apply both equilibrium (based on the Green–Kubo formulation) and nonequilibrium (based on the application of an external force to generate an explicit velocity field) algorithms. Single- and two-site models are explored for CO2, and while for volumetric properties both models provide good results, only the model that aligns with the molecular shape is found to be robust when describing highly asymmetric binary mixtures over wide ranges of temperature and pressure. While the models provide good quantitative predictions of viscosity, deviations among the algorithms and with experimental data are encountered for binary mixtures involving longer chain fluids, and in particular at high-pressure and low-temperature states.
Di Lecce S, Kornyshev AA, Urbakh M, et al., 2020, Electrotunable lubrication with ionic liquids: the effects of cation chain length and substrate polarity., ACS Applied Materials and Interfaces, Vol: 12, Pages: 4105-4113, ISSN: 1944-8244
Electrotunable lubrication with ionic liquids (ILs) provides dynamic control of friction with the prospect to achieve superlubrication. We investigate the dependence of the frictional and structural forces with 1-n,2-methyl-imidazolium tetrafluoroborate [C n MIM]+[BF4]- (n = 2, 4, 6) ILs as a lubricant on the molecular structure of the liquid, normal load, and polarity of the electrodes. Using non-equilibrium molecular dynamics simulations and coarse-grained force-fields, we show that the friction force depends significantly on the chain length of the cation. ILs containing cations with shorter aliphatic chains show lower friction forces, ∼40% for n = 2 as compared to the n = 6 case, and more resistance to squeeze-out by external loads. The normal load defines the dynamic regime of friction, and it determines maxima in the friction force at specific surface charges. At relatively low normal loads, ∼10 MPa, the velocity profile in the confined region resembles a Couette type flow, whereas at high loads, >200 MPa, the motion of the ions is highly correlated and the velocity profile resembles a "plug" flow. Different dynamic regimes result in distinctive slippage planes, located either at the IL-electrode interface or in the interior of the film, which ultimately lead, at high loads, to the observation of maxima in the friction force at specific surface charge densities. Instead, at low loads the maxima are not observed, and the friction is found to monotonously increase with the surface charge. Friction with [C n MIM]+[BF4]- as a lubricant is reduced when the liquid is confined between positively charged electrodes. This is due to better lubricating properties and enhanced resistance to squeeze out when the anion [BF4]- is in direct contact with the electrode.
Fajardo OY, Di Lecce S, Bresme F, 2020, Molecular dynamics simulation of imidazolium CnMIM-BF4 ionic liquids using a coarse grained force-field., Physical Chemistry Chemical Physics, Vol: 22, Pages: 1682-1692, ISSN: 1463-9076
Ionic liquids feature thermophysical properties that are of interest in solvents, energy storage materials and tunable lubrication applications. Here we use new Coarse Grained (CG) models to investigate the structure, dynamics and interfacial properties of the [C2-8MIM][BF4] family of ionic liquids (ILs). The simulated equation of state and diffusion coefficients are in good agreement with experimental data and with all-atom force-fields. We quantify the nano-structure and liquid-vapour interfacial properties of the ILs as a function of the size of the imidazolium cation. The computational efficiency of the CG models enables the simulation of very long time scales (100's of nanoseconds), which are needed to resolve the dynamic and interfacial properties of ILs containing cations with long aliphatic chains. For [C>4MIM] [BF4] the break in symmetry associated to the liquid-vapour interface induces nanostructuring of polar and non-polar domains in the direction perpendicular to the interface plane, with the inhomogeneous regions penetrating deep inside the bulk liquid, typically 5 nm for C8MIM cations.
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