Deconstructing temperature gradients across fluid interfaces: the structural origin of the thermal resistance of liquid-vapor interfaces

The interfacial thermal resistance determines condensation-evaporation processes and thermal transport across material-fluid interfaces. Despite its importance in transport processes, the interfacial structure responsible for the thermal resistance is still unknown. By combining non-equilibrium molecular dynamics simulations and interfacial analyses that remove the interfacial thermal fluctuations we show that the thermal resistance of liquid-vapor interfaces is connected to a low density fluid layer that is adsorbed at the liquid surface. This thermal resistance layer (TRL) defines the boundary where the thermal transport mechanism changes from that of gases (ballistic) to that characteristic of dense liquids, dominated by frequent particle collisions involving very short mean free paths. We show that the thermal conductance is proportional to the number of atoms adsorbed in the TRL, and hence we explain the structural origin of the thermal resistance in liquid-vapor interfaces.Comment: 4 pages, 4 figures, and supplementary informatio

The influence of surface roughness on the adhesive interactions and phase behavior of suspensions of calcite nanoparticles

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

Solvent-mediated interactions between nanoparticles at fluid interfaces

We investigate the solvent mediated interactions between nanoparticles adsorbed at a liquid-vapor interface in comparison to the solvent mediated interactions in the bulk liquid and vapor phases of a Lennard-Jones solvent. Molecular dynamics simulation data for the latter are in good agreement with results from integral equations in the reference functional approximation and a simple geometric approximation. Simulation results for the solvent mediated interactions at the interface differ markedly from the interactions of the particles in the corresponding bulk phases. We find that at short interparticle distances the interactions are considerably more repulsive than those in either bulk phase. At long interparticle distances we find evidence for a long-ranged attraction. We discuss these observations in terms of interfacial interactions, namely, the three-phase line tension that would operate at short distances, and capillary wave interactions for longer interparticle distances.Comment: 22 pages, 6 figure

Polarisation of water under thermal fields: the effect of the molecular dipole and quadrupole moments.

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

Thermophysical properties of water using reactive force fields.

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

Mass dipole contribution to the isotopic Soret effect in molecular mixtures

Temperature gradients induce mass separation in mixtures in a process called thermal diffusion and are quantified by the Soret coefficient ST. Thermal diffusion in fluid mixtures has been interpreted recently in terms of the so-called (pseudo-)isotopic Soret effect but only considering the mass and moment of inertia differences of the molecules. We demonstrate that the first moment of the molecular mass distribution, the mass dipole, contributes significantly to the isotopic Soret effect. To probe this physical effect, we investigate fluid mixtures consisting of rigid linear molecules that differ only by the first moment of their mass distributions. We demonstrate that such mixtures have non-zero Soret coefficients in contrast with ST = 0 predicted by current formulations. For the isotopic mixtures investigated in this work, the dependence of ST on the mass dipole arises mainly through the thermal diffusion coefficient DT. In turn, DT is correlated with the dependence of the molecular librational modes on the mass dipole. We examine the interplay of the mass dipole and the moment of inertia in defining the isotopic Soret effect and propose empirical equations that include the mass dipole contribution