Large scale and linear scaling DFT with the CONQUEST code.

We survey the underlying theory behind the large-scale and linear scaling density functional theory code, conquest, which shows excellent parallel scaling and can be applied to thousands of atoms with diagonalization and millions of atoms with linear scaling. We give details of the representation of the density matrix and the approach to finding the electronic ground state and discuss the implementation of molecular dynamics with linear scaling. We give an overview of the performance of the code, focusing in particular on the parallel scaling, and provide examples of recent developments and applications.

From cellulose to kerogen: molecular simulation of a geological process.

The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man's land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

Lattice Vibrations Change the Solid Solubility of an Alloy at High Temperatures.

We develop a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti_{1-x}Al_{x}N alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy corresponding to the true equilibrium state of the system. We demonstrate that the vibrational contribution including anharmonicity and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti_{1-x}Al_{x}N alloy, lowering the maximum temperature for the miscibility gap from 6560 to 2860 K. Our local chemical composition measurements on thermally aged Ti_{0.5}Al_{0.5}N alloys agree with the calculated phase diagram.

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.

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

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.

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.

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.

The microscopic features of heterogeneous ice nucleation may affect the macroscopic morphology of atmospheric ice crystals.

It is surprisingly difficult to freeze water. Almost all ice that forms under "mild" conditions (temperatures > -40 degrees C) requires the presence of a nucleating agent--a solid particle that facilitates the freezing process--such as clay mineral dust, soot or bacteria. In a computer simulation, the presence of such ice nucleating agents does not necessarily alleviate the difficulties associated with forming ice on accessible timescales. Nevertheless, in this work we present results from molecular dynamics simulations in which we systematically compare homogeneous and heterogeneous ice nucleation, using the atmospherically important clay mineral kaolinite as our model ice nucleating agent. From our simulations, we do indeed find that kaolinite is an excellent ice nucleating agent but that contrary to conventional thought, non-basal faces of ice can nucleate at the basal face of kaolinite. We see that in the liquid phase, the kaolinite surface has a drastic effect on the density profile of water, with water forming a dense, tightly bound first contact layer. Monitoring the time evolution of the water density reveals that changes away from the interface may play an important role in the nucleation mechanism. The findings from this work suggest that heterogeneous ice nucleating agents may not only enhance the ice nucleation rate, but also alter the macroscopic structure of the ice crystals that form.

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.