Directionally asymmetric self-assembly of cadmium sulfide nanotubes using porous alumina nanoreactors: Need for chemohydrodynamic instability at the nanoscale

We explore nanoscale hydrodynamical effects on synthesis and self-assembly of cadmium sulfide nanotubes oriented along one direction. These nanotubes are synthesized by horizontal capillary flow of two different chemical reagents from opposite directions through nanochannels of porous anodic alumina which are used primarily as nanoreactors. We show that uneven flow of different chemical precursors is responsible for directionally asymmetric growth of these nanotubes. On the basis of structural observations using scanning electron microscopy, we argue that chemohydrodynamic convective interfacial instability of multicomponent liquid-liquid reactive interface is necessary for sustained nucleation of these CdS nanotubes at the edges of these porous nanochannels over several hours. However, our estimates clearly suggest that classical hydrodynamics cannot account for the occurrence of such instabilities at these small length scales. Therefore, we present a case which necessitates further investigation and understanding of chemohydrodynamic fluid flow through nanoconfined channels in order to explain the occurrence of such interfacial instabilities at nanometer length scales.Comment: 26 pages, 6 figures; http://www.iiserpune.ac.in/researchhighlight

High temperature condensate clouds in super-hot Jupiter atmospheres

Deciphering the role of clouds is central to our understanding of exoplanet atmospheres, as they have a direct impact on the temperature and pressure structure, and observational properties of the planet. Super-hot Jupiters occupy a temperature regime similar to low mass M-dwarfs, where minimal cloud condensation is expected. However, observations of exoplanets such as WASP-12b (Teq ~ 2500 K) result in a transmission spectrum indicative of a cloudy atmosphere. We re-examine the temperature and pressure space occupied by these super-hot Jupiter atmospheres, to explore the role of the initial Al- and Ti-bearing condensates as the main source of cloud material. Due to the high temperatures a majority of the more common refractory material is not depleted into deeper layers and would remain in the vapor phase. The lack of depletion into deeper layers means that these materials with relatively low cloud masses can become significant absorbers in the upper atmosphere. We provide condensation curves for the initial Al- and Ti-bearing condensates that may be used to provide quantitative estimates of the effect of metallicity on cloud masses, as planets with metal-rich hosts potentially form more opaque clouds because more mass is available for condensation. Increased metallicity also pushes the point of condensation to hotter, deeper layers in the planetary atmosphere further increasing the density of the cloud. We suggest that planets around metal-rich hosts are more likely to have thick refractory clouds, and discuss the implication on the observed spectra of WASP-12b.Comment: Accepted for publication in MNRAS, 10 pages, 1 table, 5 figure

Unique thermodynamic relationships for ΔfHo and ΔfGo for crystalline inorganic salts. I, Predicting the possible existence and synthesis of Na2SO2 and Na2SeO2

The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M2S subnets of M2SOx (x = 3, 4) compounds (M = Na, K) when compared with the structures (room- and high-pressure phases) of their parent M2S 'alloy' [Martinez-Cruz et al. (1994), J. Solid State Chem. 110, 397-398; Vegas (2000), Crystallogr. Rev. 7, 189-286; Vegas et al. (2002), Solid State Sci. 4, 1077-1081]. These structural changes suggest that if M2SO2 would exist, its cation array might well have an anti-CaF2 structure. On the other hand, in an analysis of the existing thermodynamic data for M2S, M2SO3 and M2SO4 we have identified, and report, a series of unique linear relationships between the known Delta H-f(o) and Delta(f)G(o) values of the alkali metal (M) sulfide (x = 0) and their oxyanion salts M2SOx (x = 3 and 4), and the similarly between M2S2 disulfide (x = 0) and disulfur oxyanion salts M2S2Ox (x = 3, 4, 5, 6 and 7) and the number of O atoms in their anions x. These linear relationships appear to be unique to sulfur compounds and their inherent simplicity permits us to interpolate thermochemical data (Delta H-f(o)) for as yet unprepared compounds, M2SO (x = 1) and M2SO2 (x = 2). The excellent linearity indicates the reliability of the interpolated data. Making use of the volume-based thermodynamics, VBT [Jenkins et al. (1999), Inorg. Chem. 38, 3609-3620], the values of the absolute entropies were estimated and from them, the standard Delta S-f(o) values, and then the Delta(f)G(o) values of the salts. A tentative proposal is made for the synthesis of Na2SO2 which involves bubbling SO2 through a solution of sodium in liquid ammonia. For this attractive thermodynamic route, we estimate Delta G(o) to be approximately -500 kJ mol(-1). However, examination of the stability of Na2SO2 raises doubts and Na2SeO2 emerges as a more attractive target material. Its synthesis is likely to be easier and it is stable to disproportionation into Na2S and Na2SeO4. Like Na2SO2, this compound is predicted to have an anti-CaF2 Na2Se subnet

One-dimensional multicomponent Fermi gas in a trap: quantum Monte Carlo study

One-dimensional world is very unusual as there is an interplay between quantum statistics and geometry, and a strong short-range repulsion between atoms mimics Fermi exclusion principle, fermionizing the system. Instead, a system with a large number of components with a single atom in each, on the opposite acquires many bosonic properties. We study the ground-state properties a multi-component Fermi gas trapped in a harmonic trap by fixed-node diffusion Monte Carlo method. We investigate how the energetic properties (energy, contact) and correlation functions (density profile and momentum distribution) evolve as the number of components is changed. It is shown that the system fermionizes in the limit of strong interactions. Analytical expression are derived in the limit of weak interactions within the local density approximation for arbitrary number of components and for one plus one particle using an exact solution.Comment: 15 pages, 5 figure

Structural properties of various sodium thiogermanate glasses through DFT-based molecular dynamics simulations

We present a study of the structural properties of (x)Na$_2$S-(1-x)GeS$_2$ glasses through DFT-based molecular dynamics simulations, at different sodium concentrations ($0<x<0.5$). We computed the radial pair correlation functions as well as the total and partial structure factors. We also analyzed the evolution of the corner- and edge-sharing intertetrahedral links with the sodium concentration and show that the sodium ions exclusively destroy the former. With the increase of the sodium concentration the ``standard'' FSDP disappears and a new pre-peak appears in the structure factor which can be traced back in the Na-Na partial structure factor. This self organization of the sodium ions is coherent with Na-rich zones that we find at high modifier concentration.Comment: 9 pages, 7 figures; to be published in Phys. Rev.

Sulfide- and nitrite-dependent nitric oxide production in the intestinal tract

In the gut ecosystem, nitric oxide (NO) has been described to have damaging effects on the energy metabolism of colonocytes. Described mechanisms of NO production are microbial reduction of nitrate via nitrite to NO and conversion of l-arginine by NO synthase. The aim of this study was to investigate whether dietary compounds can stimulate the production of NO by representative cultures of the human intestinal microbiota and whether this correlates to other processes in the intestinal tract. We have found that the addition of a reduced sulfur compound, i.e. cysteine, contributed to NO formation. This increase was ascribed to higher sulfide concentrations generated from cysteine that in turn promoted the chemical conversion of nitrite to NO. The NO release from nitrite was of the order of 4 parts per thousand at most. Overall, it was shown that two independent biological processes contribute to the chemical formation of NO in the intestinal tract: (i) the production of sulfide by fermentation of sulfur containing amino acids or reduction of sulfate by sulfate reducing bacteria, and (ii) the reduction of nitrate to nitrite. Our results indicate that dietary thiol compounds in combination with nitrate may contribute to colonocytes damaging processes by promoting NO formation

Chemically triggered formation of two-dimensional epitaxial quantum dot superlattices

Two dimensional superlattices of epitaxially connected quantum dots enable size-quantization effects to be combined with high charge carrier mobilities, an essential prerequisite for highly performing QD devices based on charge transport. Here, we demonstrate that surface active additives known to restore nanocrystal stoichiometry can trigger the formation of epitaxial superlattices of PbSe and PbS quantum dots. More specifically, we show that both chalcogen-adding (sodium sulfide) and lead oleate displacing (amines) additives induce small area epitaxial superlattices of PbSe quantum dots. In the latter case, the amine basicity is a sensitive handle to tune the superlattice symmetry, with strong and weak bases yielding pseudohexagonal or quasi-square lattices, respectively. Through density functional theory calculations and in situ titrations monitored by nuclear magnetic resonance spectroscopy, we link this observation to the concomitantly different coordination enthalpy and ligand displacement potency of the amine. Next to that, an initial similar to 10% reduction of the initial ligand density prior to monolayer formation and addition of a mild, lead oleate displacing chemical trigger such as aniline proved key to induce square superlattices with long-range, square micrometer order; an effect that is the more pronounced the larger the quantum dots. Because the approach applies to PbS quantum dots as well, we conclude that it offers a reproducible and rational method for the formation of highly ordered epitaxial quantum dot superlattices

Berezinskii-Kosterlitz-Thouless transition in two-dimensional dipole systems

The superfluid to normal fluid transition of dipolar bosons in two dimensions is studied throughout the whole density range using path integral Monte Carlo simulations and summarized in the phase diagram. While at low densities, we find good agreement with the universal results depending only on the scattering length $a_s$, at moderate and high densities, the transition temperature is strongly affected by interactions and the elementary excitation spectrum. The results are expected to be of relevance to dipolar atomic and molecular systems and indirect excitons in quantum wells

Non-Universal Equation of State of the Two-Dimensional Bose Gas

For a dilute two-dimensional Bose gas the universal equation of state has a logarithmic dependence on the s-wave scattering length. Here we derive non-universal corrections to this equation of state taking account finite-range effects of the inter-atomic potential. Our beyond-mean-field analytical results are obtained performing dimensional regularization of divergent zero-point quantum fluctuations within the finite-temperature formalism of functional integration. In particular, we find that in the grand canonical ensemble the pressure has a nonpolynomial dependence on the finite- range parameter and it is a highly nontrivial function of chemical potential and temperature.Comment: 5 pages, to be published in Phys. Rev. Let

Synthesis and catalytic properties of copper(II) 1-aryl-5-benzothiazolylformazanates

New copper(II) benzothiazolylformazane complexes were synthesized and immobilized on AN-18 anion exchanger. The influence of the composition of the coordination core of copper(II) benzthiazolylformazanates and temperature on their catalytic properties in decomposition of H2O2 and oxidation of Na2S in aqueous solution was studied