Chemomechanical equilibrium at the interface between a simple elastic solid and its liquid phase.

Applying diffusion coupled deformation theory, we investigate how the elastic properties of a solid body are modified when forced to keep its chemical potential aligned with that of its melt. The theory is implemented at the classical level of continuum mechanics, treating materials as simple continua defined by uniform constitutive relations. A phase boundary is a sharp dividing surface separating two continua in mechanical and chemical equilibrium. We closely follow the continuum theory of the swelling of elastomers (gels) but now applied to a simple two phase one-component system. The liquid is modeled by a local free energy density defining a chemical potential and hydrostatic pressure as usual. The model is extended to a solid by adding a non-linear shear elastic energy term with an effective modulus depending on density. Imposing chemomechanical equilibrium with the liquid reservoir reduces the bulk modulus of the solid to zero. The shear modulus remains finite. The stability of the hyper-compressible solid is investigated in a thought experiment. A mechanical load is applied to a rectangular bar under the constraint of fixed lateral dimensions. The linear elastic modulus for axial loading is evaluated and found to be larger than zero, implying that the bar, despite the zero bulk modulus, can support a weight placed on its upper surface. The weight is stabilized by the induced shear stress. The density dependence of the shear modulus is found to be a second order effect reducing the density of the stressed solid (chemostriction)

Electromechanics of the liquid water vapour interface.

Two collective properties distinguishing the thin liquid water vapour interface from the bulk liquid are the anisotropy of the pressure tensor giving rise to surface tension and the orientational alignment of the molecules leading to a finite dipolar surface potential. Both properties can be regarded as capillary phenomena and are likely to be coupled. We have investigated this coupling by determining the response of the tangential component of the surface tension to the application of an electric field normal to the surface using finite field molecular dynamics simulations. We find an upside down parabola with a maximum shifted away from zero field. Comparing the molecular dynamics results to a phenomenological electromechanical model we relate the zero field derivative of the tangential part of the surface tension to the electrostatic potential generated by the spontaneous interface polarization. When interpreted with this model our simulations also indicate that Kelvin forces due to electric field gradients at a polarized interface play an important role in the effective dielectric response

Computing the Kirkwood g-Factor by Combining Constant Maxwell Electric Field and Electric Displacement Simulations: Application to the Dielectric Constant of Liquid Water.

In his classic 1939 paper, Kirkwood linked the macroscopic dielectric constant of polar liquids to the local orientational order as measured by the g-factor (later named after him) and suggested that the corresponding dielectric constant at short-range is effectively equal to the macroscopic value just after "a distance of molecular magnitude" [ Kirkwood, J. Chem. Phys., 1939, 7, 911 ]. Here, we show a simple approach to extract the short-ranged Kirkwood g-factor from molecular dynamics (MD) simulation by superposing the outcomes of constant electric field E and constant electric displacement D simulations [ Zhang and Sprik, Phys. Rev. B: Condens. Matter Mater. Phys., 2016, 93, 144201 ]. Rather than from the notoriously slow fluctuations of the dipole moment of the full MD cell, the dielectric constant can now be estimated from dipole fluctuations at short-range, accelerating the convergence. Exploiting this feature, we computed the bulk dielectric constant of liquid water modeled in the generalized gradient approximation (PBE) to density functional theory and found it to be at least 40% larger than the experimental value.The research fellowship (Grant ZH 477/1-1) awarded to C.Z. by the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged. Computational resources were provided by the UK Car−Parrinello (UKCP) consortium funded by the Engineering and Physical Sciences Research Council (EPSRC).This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.jpclett.6b0112

Coupling of surface chemistry and electric double layer at TiO2_2 electrochemical interfaces

We used the latest development in density functional theory based finite-field molecular dynamics simulation to investigate pH-dependence of the Helmholtz capacitance at electrified rutile TiO$_2$ (110)-NaCl electrolyte interfaces. It is found that, due to competing forces from surface adsorption and from the electric double layer, water molecules undergo rapid adsorption-desorption at high pH and leads to a much larger capacitance. It is also seen that, proton transfer at low pH increases significantly the capacitance value. These elucidate the microscopic origin for the same trend observed in titration experiments

Aqueous transition-metal cations as impurities in a wide gap oxide: the Cu(2+)/Cu(+) and Ag(2+)/Ag(+) redox couples revisited.

The interactions of the d electrons of transition-metal aqua ions with the solvent are usually divided in short-range electronic interactions with ligand water molecules and long-range electrostatic interactions with molecules beyond the first coordination shell. This is the rationale behind the cluster continuum and QM/MM methods developed for the computation of the redox potentials. In the density functional theory based molecular dynamics (DFTMD) method, the electronic states of the complex are also allowed to mix with the extended band states of the solvent. Returning to the Cu(+) and Ag(+) oxidation reaction, which has been the subject of DFTMD simulation before, we show that coupling to the valence band states of water is greatly enhanced by the band gap error in the density functional approximation commonly used in DFTMD (the generalized gradient approximation). This effect is analyzed by viewing the solvent as a wide gap oxide and the redox active ions as electronic defects. The errors can be reduced significantly by application of hybrid functionals containing a fraction of Hartree-Fock exchange. These calculations make use of recent progress in DFTMD technology, enabling us to include sp core polarization and Hartree-Fock exchange in condensed-phase model systems.We acknowledge grants from the National Science Foundation of China (Nos. 41002013, 41222015 and 41273074) and Newton International Fellowship program. Further support came from the State Key Laboratory for Mineral Deposits Research in Nanjing University and the Foundation for the Author of National Excellent Doctoral Dissertation of PR China (No.201228).This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/jp506691h

Acidity of edge surface sites of montmorillonite and kaolinite

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