Zamaan Raza

Proton ordering in cubic ice and hexagonal ice; a potential new ice phase—XIc

Ordinary water ice forms under ambient conditions and has two polytypes, hexagonal ice (Ih) and cubic ice (Ic). From a careful comparison of proton ordering arrangements in Ih and Ic using periodic density functional theory (DFT) and diffusion Monte Carlo (DMC) approaches, we find that the most stable arrangement of water molecules in cubic ice is isoenergetic with that of the proton ordered form of hexagonal ice (known as ice XI). We denote this potential new polytype of ice XI as XIc and discuss a possible route for preparing ice XIc.

On the Formation of Glycolaldehyde in Dense Molecular Cores

Glycolaldehyde is a simple monosaccharide sugar linked to prebiotic chemistry. Recently, it was detected in a molecular core in the star-forming region G31.41+0.31 at a reasonably high abundance. We investigate the formation of glycolaldehyde at 10 K to determine whether it can form efficiently under typical dense core conditions. Using an astrochemical model, we test five different reaction mechanisms that have been proposed in the astrophysical literature, finding that a gas-phase formation route is unlikely. Of the grain-surface formation routes, only two are efficient enough at very low temperatures to produce sufficient glycolaldehyde to match the observational estimates, with the mechanism culminating in CH3OH + HCO being favored. However, when we consider the feasibility of these mechanisms from a reaction chemistry perspective, the second grain-surface route looks more promising, H3CO + HCO.

GLYCOLALDEHYDE FORMATION VIA THE DIMERIZATION OF THE FORMYL RADICAL

Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints.

High Energy Density Mixed Polymeric Phase from Carbon Monoxide and Nitrogen

Carbon monoxide and nitrogen are among the potentially interesting high-energy density materials. However, in spite of the physical similarities of the molecules, they behave very differently at high pressures. Using density functional theory and structural prediction methods, we examine the ability of these systems to combine their respective properties and form novel mixed crystalline phases under pressures of up to 100 GPa. Interestingly, we find that CO catalyzes the molecular dissociation of N2, which means mixed structures are favored at a relatively low pressure (below 18 GPa), and that a three-dimensional framework with Pbam symmetry becomes the most stable phase above 52 GPa, i.e., at much milder conditions than in pure solid nitrogen. This structure is dynamically stable at ambient pressure and has an energy density of approximately 2.2  kJ g(-1), making it a candidate for a high-energy density material, and one that could be achieved at less prohibitive experimental conditions.

Novel superconducting skutterudite-type phosphorus nitride at high pressure from first-principles calculations

State of the art variable composition structure prediction based on density functional theory demonstrates that two new stoichiometries of PN, PN3 and PN2, become viable at high pressure. PN3 has a skutterudite-like Immm structure and is metastable with positive phonon frequencies at pressures between 10 and 100 GPa. PN3 is metallic and is the first reported nitrogen-based skutterudite. Its metallicity arises from nitrogen p-states which delocalise across N4 rings characteristic of skutterudites, and it becomes a good electron-phonon superconductor at 10 GPa, with a Tc of around 18 K. The superconductivity arises from strongly enhanced electron-phonon coupling at lower pressures, originating primarily from soft collective P-N phonon modes. The PN2 phase is an insulator with P2/m symmetry and is stable at pressures in excess of 200 GPa.

Effect of salt on the H-bond symmetrization in ice.

Significance Ice-VII and ice-X phases are the most stable forms of ice at high temperature and extreme pressures, typical of the interiors of satellites and planets. The phase transition between them is a prototypical case of quantum-driven phenomenon, as it can be described as a quantum delocalization of protons in the middle of O–O distances. In this study, we investigate the effect of ions on such quantum effects. We show that the presence of ions significantly modifies the fundamental H-bond properties of water ices. This finding could challenge our present description of the physics of ice bodies, essentially based on the assumption of the properties of pure ice under high pressure. The richness of the phase diagram of water reduces drastically at very high pressures where only two molecular phases, proton-disordered ice VII and proton-ordered ice VIII, are known. Both phases transform to the centered hydrogen bond atomic phase ice X above about 60 GPa, i.e., at pressures experienced in the interior of large ice bodies in the universe, such as Saturn and Neptune, where nonmolecular ice is thought to be the most abundant phase of water. In this work, we investigate, by Raman spectroscopy up to megabar pressures and ab initio simulations, how the transformation of ice VII in ice X is affected by the presence of salt inclusions in the ice lattice. Considerable amounts of salt can be included in ice VII structure under pressure via rock–ice interaction at depth and processes occurring during planetary accretion. Our study reveals that the presence of salt hinders proton order and hydrogen bond symmetrization, and pushes ice VII to ice X transformation to higher and higher pressures as the concentration of salt is increased.

Temperature-dependent elastic properties of Ti1−xAlxN alloys

Ti1−xAlxN is a technologically important alloy that undergoes a process of high temperature age-hardening that is strongly influenced by its elastic properties. We have performed first principles c ...

Computer simulations of glasses: the potential energy landscape.

We review the current state of research on glasses, discussing the theoretical background and computational models employed to describe them. This article focuses on the use of the potential energy landscape (PEL) paradigm to account for the phenomenology of glassy systems, and the way in which it can be applied in simulations and the interpretation of their results. This article provides a broad overview of the rich phenomenology of glasses, followed by a summary of the theoretical frameworks developed to describe this phenomonology. We discuss the background of the PEL in detail, the onerous task of how to generate computer models of glasses, various methods of analysing numerical simulations, and the literature on the most commonly used model systems. Finally, we tackle the problem of how to distinguish a good glass former from a good crystal former from an analysis of the PEL. In summarising the state of the potential energy landscape picture, we develop the foundations for new theoretical methods that allow the ab initio prediction of the glass-forming ability of new materials by analysis of the PEL.