Mark Calleja

Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6]

We show that silver(I) hexacyanocobaltate(III), Ag3[Co(CN)6], exhibits positive and negative thermal expansion an order of magnitude greater than that seen in other crystalline materials. This framework material expands along one set of directions at a rate comparable to the most weakly bound solids known. By flexing like lattice fencing, the framework couples this to a contraction along a perpendicular direction. This gives negative thermal expansion that is 14 times larger than in ZrW2O8. Density functional theory calculations quantify both the low energy associated with this flexibility and the role of argentophilic (Ag+...Ag+) interactions. This study illustrates how the mechanical properties of a van der Waals solid might be engineered into a rigid, useable framework.

Trapping of oxygen vacancies on twin walls of CaTiO3: a computer simulation study

We have studied the atomic structure of [001]90 ◦ rotation twin walls in orthorhombic CaTiO3 (symmetry Pbnm )a t low temperature (10 K) and their effects on oxygen vacancies. The wall thickness was found to be 2.3 nm at

Anisotropic ionic transport in quartz: the effect of twin boundaries

Transport of Na+ and Li+ under the influence of an electric field in twinned quartz is simulated using molecular dynamics techniques. Comparison between bulk transport and transport along twin boundaries shows that the cations are trapped inside twin walls for weak fields along the crystallographic c-axis. Stronger fields lead to transport along twin walls with significantly lower mobility than in the bulk. With E along [110], transport in the wall is faster than in the bulk. We observe cation trapping preferentially in the twin walls when E is applied out of the plane of the wall.

Origin of the colossal positive and negative thermal expansion in Ag3[Co(CN)6]: an ab initio density functional theory study

DFT calculations have been used to provide insights into the origin of the colossal positive and negative thermal expansion in Ag3[Co(CN)6]. The results confirm that the positive expansion within the trigonal basal plane and the negative expansion in the orthogonal direction are coupled due to the existence of a network defined by nearly rigid bonds within the chains of Co–C–N–Ag–N–C–Co linkages. The origin of the colossal values of the coefficients of thermal expansion arise from an extremely shallow energy surface that allows a flexing of the structure with small energy cost. The thermal expansion can be achieved with a modest value of the overall Gruneisen parameter. The energy surface is so shallow that we need to incorporate a small empirical dispersive interaction to give ground-state lattice parameters that match experimental values at low temperature. We compare the results with DFT calculations on two isostructural systems: H3[Co(CN)6], which is known to have much smaller values of the coefficients of thermal expansion, and Au3[Co(CN)6], which has not yet been synthesized but which is predicted by our calculations to be another candidate material for showing colossal positive and negative thermal expansion.

Structural and magnetic phase transitions in simple oxides using hybrid functionals

We present the structural as well as elastic properties of the alkaline earth oxides and FeO, calculated using hybrid exchange functionals within DFT. We show that by empirically fitting the amount of Fock-exchange in the hybrid functionals, we can accurately reproduce the pressure-induced phase transitions for MgO, CaO, SrO and BaO. For FeO the hybrid functionals predict an insulator↔metal transition at ca. 150 GPa, associated with an i-B8↔B8 structural phase transition. The structural phase transition is accompanied by a spin transition from a high- to low-spin electron configuration on the Fe2+ ions. Hence, FeO undergoes a magnetic phase transition from an anti-ferromagnetic to non-magnetic structure. We also find that as the ionicity of the polymorphs increases a higher fraction of Fock-exchange is required to reproduce the structural volumes reported from experiments.

Collaborative grid infrastructure for molecular simulations: The eMinerals minigrid as a prototype integrated compute and data grid

This paper describes a prototype grid infrastructure, called the “eMinerals minigrid”, for molecular simulation scientists. which is based on an integration of shared compute and data resources. We describe the key components, namely the use of Condor pools, Linux/Unix clusters with PBS and IBMs LoadLeveller job handling tools, the use of Globus for security handling, the use of Condor-G tools for wrapping globus job submit commands, Condors DAGman tool for handling workflow, the Storage Resource Broker for handling data, and the CCLRC dataportal and associated tools for both archiving data with metadata and making data available to other workers.

New tools to support collaboration and virtual organizations

We describe the use of new eScience tools to support collaboration, including the use of XML data representations to support shared viewing of the information content of data, metadata tools for documenting data and Web 2.0 social networking tools for documenting ideas and the collaboration process. This latter work has led to the development of the http://SciSpace.net Web resource.

Ab-initio simulations of magnetic iron sulphides

We present the results of simulations, using density functional theory (DFT) with generalized gradient corrections (GGA), on the troilite (FeS), pyrrhotite (Fe1−xS) and MnP phases of FeS. The values obtained for the cell parameters and c/a ratio of troilite accurate to within 1% of those determined by experiment, a significant improvement on previous simulations. Energy–volume curves for FeS in the troilite and MnP structures indicate a pressure-induced transition at 4 GPa (experimentally observed at 3.4 GPa). Comparison of spin-polarised and non-spin-polarised simulations of the troilite structure demonstrate the significance of magnetostructural effects in determining the c/a ratio and shed light on the magnetic and volume collapse of FeS on its transition from the MnP to a monoclinic structure at 6.7 GPa. Simulations of different (001) surface terminations of troilite indicate that stable surfaces are characterised by triangles of iron atoms “capped” with a sulphur atom.

eScience for molecular-scale simulations and the eMinerals project

We review the work carried out within the eMinerals project to develop eScience solutions that facilitate a new generation of molecular-scale simulation work. Technological developments include integration of compute and data systems, developing of collaborative frameworks and new researcher-friendly tools for grid job submission, XML data representation, information delivery, metadata harvesting and metadata management. A number of diverse science applications will illustrate how these tools are being used for large parameter-sweep studies, an emerging type of study for which the integration of computing, data and collaboration is essential.

Performance prediction for running workflows under role-based authorization mechanisms

When investigating the performance of running scientific/commercial workflows in parallel and distributed systems, we often take into account only the resources allocated to the tasks constituting the workflow, assuming that computational resources will accept the tasks and execute them to completion once the processors are available. In reality, and in particular in Grid or e-business environments, security policies may be implemented in the individual organisations in which the computational resources reside. It is therefore expedient to have methods to calculate the performance of executing workflows under security policies. Authorisation control, which specifies who is allowed to perform which tasks when, is one of the most fundamental security considerations in distributed systems such as Grids. Role-Based Access Control (RBAC), under which the users are assigned to certain roles while the roles are associated with prescribed permissions, remains one of the most popular authorisation control mechanisms. This paper presents a mechanism to theoretically compute the performance of running scientific workflows under RBAC authorisation control. Various performance metrics are calculated, including both system-oriented metrics, (such as system utilisation, throughput and mean response time) and user-oriented metrics (such as mean response time of the workflows submitted by a particular client). With this work, if a client informs an organisation of the workflows they are going to submit, the organisation is able to predict the performance of these workflows running in its local computational resources (e.g. a high-performance cluster) enforced with RBAC authorisation control, and can also report client-oriented performance to each individual user.