Early Oxidation Processes on the Greigite Fe₃S⁴(001) Surface by Water: A Density Functional Theory Study

Greigite (Fe3S4), the sulfide counterpart of the spinel-structured oxide material magnetite (Fe3O4), is a mineral widely identified in anoxic aquatic environments and certain soils, which can be oxidized, thereby producing extremely acid solutions of sulfur-rich wastewaters, so-called acid mine drainage (AMD) or acid rock drainage (ARD). Here we report a computational study of the partial replacement of sulfur (forming H2S) by oxygen (from H2O) in the Fe3S4(001) surface, derived from density functional theory calculations with on-site Coulomb approach and long-range dispersion corrections (DFT+U–D2). We have proposed three pathways for the oxidation of the surface as a function of H2O coverage and pH. Different pathways give different intermediates, some of which are followed by a solid-state diffusion of the O atom. Low levels of H2O coverage, and especially basic conditions, seem to be essential, leading to the most favorable energetic landscape for the oxidation of the Fe3S4(001) surface. We have derived the thermodynamic and kinetic profile for each mechanism and plotted the concentration of H2S and protons in aqueous solution and thermodynamic equilibrium with the stoichiometric and partially oxidized Fe3S4(001) surface as a function of the temperature. Changes in the calculated vibrational frequencies of the adsorbed intermediates are used as a means to characterize their transformation. We have taken into account statistical entropies for H2S and H2O and other experimental parameters, showing that this mineral may well be among those responsible for the generation of AMD

Theory for Bose-Einstein condensation of light in nano-fabricated semiconductor microcavities

We construct a theory for Bose-Einstein condensation of light in nano-fabricated semiconductor microcavities. We model the semiconductor by one conduction and one valence band which consist of electrons and holes that interact via a Coulomb interaction. Moreover, we incorporate screening effects by using a contact interaction with the scattering length for a Yukawa potential and describe in this manner the crossover from exciton gas to electron-hole plasma as we increase the excitation level of the semiconductor. We then show that the dynamics of the light in the microcavities is damped due to the coupling to the semiconductor. Furthermore, we demonstrate that on the electron-hole plasma side of the crossover, which is relevant for the Bose-Einstein condensation of light, this damping can be described by a single dimensionless damping parameter that depends on the external pumping. Hereafter, we propose to probe the superfluidity of light in these nano-fabricated semiconductor microcavities by making use of the differences in the response in the normal or superfluid phase to a sudden rotation of the trap. In particular, we determine frequencies and damping of the scissors modes that are excited in this manner. Moreover, we show that a distinct signature of the dynamical Casimir effect can be observed in the density-density correlations of the excited light fluid

Asymptotic Bethe equations for open boundaries in planar AdS/CFT

We solve, by means of a nested coordinate Bethe ansatz, the open-boundaries scattering theory describing the excitations of a free open string propagating in $AdS_5\times S^5$, carrying large angular momentum $J=J_{56}$, and ending on a maximal giant graviton whose angular momentum is in the same plane. We thus obtain the all-loop Bethe equations describing the spectrum, for $J$ finite but large, of the energies of such strings, or equivalently, on the gauge side of the AdS/CFT correspondence, the anomalous dimensions of certain operators built using the epsilon tensor of SU(N). We also give the Bethe equations for strings ending on a probe D7-brane, corresponding to meson-like operators in an $\mathcal N=2$ gauge theory with fundamental matter.Comment: 30 pages. v2: minor changes and discussion section added, J.Phys.A version

A DFT+U study of the oxidation of cobalt nanoparticles: Implications for biomedical applications

Nanomaterials – magnetic nanoparticles in particular have been shown to have significant potential in cancer theranostics, where iron oxides are commonly the materials of choice. While biocompatibility presents an advantage, the low magnetisation is a barrier to their widespread use. As a result, highly magnetic cobalt nanoparticles are attracting increasing attention as a promising alternative. Precise control of the physiochemical properties of such magnetic systems used in biomedicine is crucial, however, it is difficult to test their behaviour in vivo. In the present work, density functional theory calculations with the Dudarev approach (DFT+U) have been used to model the adsorption of oxygen on low Miller index surfaces of the hexagonal phase of cobalt. In vivo conditions of temperature and oxygen partial pressure in the blood have been considered, and the effects of oxidation on the overall properties of cobalt nanoparticles are described. It is shown that oxygen adsorbs spontaneously on all surfaces with the formation of non-magnetic cobalt tetroxide, Co3O4, at body temperature, confirming that, despite their promising magnetic properties, bare cobalt nanoparticles would not be suitable for biomedical applications. Surface modifications could be designed to preserve their favourable characteristics for future utilisation

DFT-D2 simulations of water adsorption and dissociation on the low-index surfaces of mackinawite (FeS)

The adsorption and dissociation of water on mackinawite (layered FeS) surfaces were studied using dispersion-corrected density functional theory (DFT-D2) calculations. The catalytically active sites for H2O and its dissociated products on the FeS {001}, {011}, {100}, and {111} surfaces were determined, and the reaction energetics and kinetics of water dissociation were calculated using the climbing image nudged elastic band technique. Water and its dissociation products are shown to adsorb more strongly onto the least stable FeS{111} surface, which presents low-coordinated cations in the surface, and weakest onto the most stable FeS{001} surface. The adsorption energies decrease in the order FeS{111} > FeS{100} > FeS{011} > FeS{001}. Consistent with the superior reactivity of the FeS{111} surface towards water and its dissociation products, our calculated thermochemical energies and activation barriers suggest that the water dissociation reaction will take place preferentially on the FeS nanoparticle surface with the {111} orientation. These findings improve our understanding of how the different FeS surface structures and the relative stabilities dictate their reactivity towards water adsorption and dissociation

Bound States of the q-Deformed AdS5 x S5 Superstring S-matrix

The investigation of the q deformation of the S-matrix for excitations on the string world sheet in AdS5 x S5 is continued. We argue that due to the lack of Lorentz invariance the situation is more subtle than in a relativistic theory in that the nature of bound states depends on their momentum. At low enough momentum |p|<E the bound states transform in the anti-symmetric representation of the super-algebra symmetry and become the solitons of the Pohlmeyer reduced theory in the relativistic limit. At a critical momentum |p|=E they become marginally unstable, and at higher momenta the stable bound states are in the symmetric representation and become the familiar magnons in the string limit as q->1. This subtlety fixes a problem involving the consistency of crossing symmetry with the relativistic limit found in earlier work. With mirror kinematics, obtained after a double Wick rotation, the bound state structure is simpler and there are no marginally unstable bound states.Comment: 25 page

Modelling the effects of salt solutions on the hydration of calcium ions

Classical molecular dynamics simulations of several aqueous alkali halide salt solutions have been used to determine the effect of electrolytes on the structure of water and the hydration properties of calcium ions. Compared with the simulations of Ca2+ ions in pure liquid water, the frequency of water exchange in the first hydration shell of calcium, which is a fundamental process in controlling the reactivity of calcium(II) aqua-ions, is drastically reduced in the presence of other electrolytes in solution. The strong stabilization of the hydration shell of Ca2+ occurs not only when the halide anions are directly coordinated to calcium, but also when the alkali and halide ions are placed at or outside the second coordination shell of Ca2+, suggesting that the reactivity of the first solvation shell of the calcium ion can be influenced by the specific affinity of other ions in solution for the water molecules coordinated to Ca2+. Analysis of the hydrogen-bonded structure of water in the vicinity of the calcium ion shows that the average number of hydrogen bonds per water molecules, which is 1.8 in pure liquid water, decreases as the concentration of alkali–halide salts in solution increases, and that the temporal fluctuations of hydrogen bonds are significantly larger than those obtained for Ca2+ in pure liquid water. This effect has been explained in terms of the dynamics of reorganization of the O–H X (X = F, Cl and Br) hydrogen bond. This work shows the importance of solution composition in determining the hydrogen-bonding network and ligand-exchange dynamics around metal ions, both in solution and at the mineral–water interfaces, which in turn has implications for interactions occurring at the mineral–water interface, ultimately controlling the mobilization of ions in the environment as well as in industrial processes

Field-induced domain wall propagation velocity in magnetic nanowires

A thory of field-induced domain wall (DW) propagation is developed. The theory not only explains why a DW in a defect-free nanowire must propagate at a finite velocity, but also provides a proper definition of DW propagation velocity. This definition, valid for an arbitrary DW structure, allows one to compute the instantaneous DW velocity in a meaningful way even when the DW is not moving as a rigid body. A new velocity-field formula beyond the Walker breakdown field, which is in excellent agreement with both experiments and numerical simulations, is derived

The Bethe Ansatz for AdS5 x S5 Bound States

We reformulate the nested coordinate Bethe ansatz in terms of coproducts of Yangian symmetry generators. This allows us to derive the nested Bethe equations for the bound state string S-matrices. We find that they coincide with the Bethe equations obtained from a fusion procedure. The bound state number dependence in the Bethe equations appears through the parameters x^{\pm} and the dressing phase only.Comment: typos correcte

Interaction of SO2 with the Platinum (001), (011), and (111) Surfaces: A DFT Study

Given the importance of SO2 as a pollutant species in the environment and its role in the hybrid sulphur (HyS) cycle for hydrogen production, we carried out a density functional theory study of its interaction with the Pt (001), (011), and (111) surfaces. First, we investigated the adsorption of a single SO2 molecule on the three Pt surfaces. On both the (001) and (111) surfaces, the SO2 had a S,O-bonded geometry, while on the (011) surface, it had a co-pyramidal and bridge geometry. The largest adsorption energy was obtained on the (001) surface (Eads = −2.47 eV), followed by the (011) surface (Eads = −2.39 and −2.28 eV for co-pyramidal and bridge geometries, respectively) and the (111) surface (Eads = −1.85 eV). When the surface coverage was increased up to a monolayer, we noted an increase of Eads/SO2 for all the surfaces, but the (001) surface remained the most favourable overall for SO2 adsorption. On the (111) surface, we found that when the surface coverage was θ > 0.78, two neighbouring SO2 molecules reacted to form SO and SO3. Considering the experimental conditions, we observed that the highest coverage in terms of the number of SO2 molecules per metal surface area was (111) > (001) > (011). As expected, when the temperature increased, the surface coverage decreased on all the surfaces, and gradual desorption of SO2 would occur above 500 K. Total desorption occurred at temperatures higher than 700 K for the (011) and (111) surfaces. It was seen that at 0 and 800 K, only the (001) and (111) surfaces were expressed in the morphology, but at 298 and 400 K, the (011) surface was present as well. Taking into account these data and those from a previous paper on water adsorption on Pt, it was evident that at temperatures between 400 and 450 K, where the HyS cycle operates, most of the water would desorb from the surface, thereby increasing the SO2 concentration, which in turn may lead to sulphur poisoning of the catalyst