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Doping is the most common strategy employed in the development of new and improved materials. However, predicting the effects of doping on the atomic-scale structure of a material is often difficult or limited to high-end experimental techniques. Doping can induce phase separation in a material, undermining the material's stability. A further complication is that dopant atoms can segregate to interfaces in a material such as grain boundaries (GBs), with consequences for key macroscopic properties of the material such as its conductivity. Here, we describe a computational methodology based on semi-grand canonical Monte Carlo which can be used to probe these phenomena at the atomic scale for metal oxide solid solutions. The methodology can provide precise predictions of the thermodynamic conditions at which phase separation occurs. It can also provide the segregation patterns exhibited by GBs at given conditions. We apply the methodology to one of the most important catalytic materials, ceria-zirconia. Our calculations reveal an interesting richness in the GB segregation in this system. Most GBs we examined exhibited continuous increases in Zr segregation upon Zr doping, with a concomitant reduction in the formation enthalpies of the GBs. However, a few GBs exhibited no segregation at low temperatures. We also observed evidence of first-order complexion transitions in some GBs.

Accurately modeling the electronic structure of materials is a persistent challenge to high-throughput screening. A promising means of balancing accuracy against computational cost are non-self-consistent calculations with hybrid density-functional theory, where the electronic band energies are evaluated using a hybrid functional from orbitals obtained with a less demanding (semi-)local functional. We have quantified the performance of this technique for predicting the physical properties of sixteen tetrahedral semiconductors with bandgaps from 0.2-5.5 eV. Provided the base functional predicts a non-metallic electronic structure, bandgaps within 5 % of the PBE0 and HSE06 gaps can be obtained with an order of magnitude reduction in computing time. The positions of the valence and conduction band extrema and the Fermi level are well reproduced, further enabling calculation of the band dispersion, density of states, and dielectric properties using Fermi's Golden Rule. While the error in the non-self-consistent total energies is ~50 meV atom-1, the energy-volume curves are reproduced accurately enough to obtain the equilibrium volume and bulk modulus with minimal error. We also test the dielectric-dependent scPBE0 functional and obtain bandgaps and dielectric constants to within 2.5 % of the self-consistent results, which amount to a significant improvement over self-consistent PBE0 for a similar computational cost. We identify cases where the non-self-consistent approach is expected to perform poorly, and demonstrate that partial self-consistency provides a practical and efficient workaround. Finally, we perform proof-of-concept calculations on CoO and NiO to demonstrate the applicability of the technique to strongly-correlated open-shell transition-metal oxides., Comment: Manuscript + Supporting Information

Classical molecular dynamics simulations are a common component of multi-modal analyses from scattering measurements, such as small-angle scattering and diffraction. Users of these experimental techniques often have no formal training in the theory and practice of molecular dynamics simulation, leading to the possibility of these simulations being treated as a "black box" analysis technique. In this article, we describe an open educational resource (OER) designed to introduce classical molecular dynamics to users of scattering methods. This resource is available as a series of interactive web pages, which can be easily accessed by students, and as an open source software repository, which can be freely copied, modified, and redistributed by educators. The topic covered in this OER includes classical atomistic modelling, parameterising interatomic potentials, molecular dynamics simulations, typical sources of error, and some of the approaches to using simulations in the analysis of scattering data., Comment: Electronic Supplementary Information (ESI) available: All analysis/plotting scripts and figure files, allowing for a fully reproducible, and automated, analysis workflow for the work presented is available at \url{https://github.com/arm61/sim_and_scat_paper} (DOI: 10.5281/zenodo.2556826) under a CC BY-SA 4.0 license

Using molecular simulation to aid in the analysis of neutron reflectometry measurements is commonplace. However, reflectometry is a tool to probe large-scale structures, and therefore the use of all-atom simulation may be irrelevant. This work presents the first direct comparison between the reflectometry profiles obtained from different all-atom and coarse-grained molecular dynamics simulations. These are compared with a traditional model layer structure analysis method to determine the minimum simulation resolution required to accurately reproduce experimental data. We find that systematic limits reduce the efficacy of the MARTINI potential model, while the Berger united-atom and Slipids all-atom potential models agree similarly well with the experimental data. The model layer structure gives the best agreement, however, the higher resolution simulation-dependent methods produce an agreement that is comparable. Finally, we use the atomistic simulation to advise on possible improvements that may be offered to the model layer structures, creating a more realistic monolayer model., Comment: Electronic Supplementary Information (ESI) available: All analysis/plotting scripts and figure files, allowing for a fully reproducible, and automated, analysis workflow for the work presented is available at \url{https://github.com/arm61/sim_vs_trad} (DOI: 10.5281/zenodo.2600729) under a CC BY-SA 4.0 license

In this work, we present the first example of the self-assembly of phospholipid monolayers at the interface between air and an ionic solvent. Deep eutectic solvents are a novel class of environmentally friendly non-aqueous room temperature liquids with tunable properties, that have wide ranging potential applications and are capable of promoting the self-assembly of surfactant molecules. We use a chemically-consistent Bayesian modelling of X-ray and neutron reflectometry measurements to show that these monolayers broadly behave as they do on water. This method allows for the monolayer structure to be determined, alongside the molecular volumes of the individual monolayer components without the need for water-specific constraints to be introduced. Furthermore, using this method we are able to better understand the correlations present between parameters in the analytical model. This example of a non-aqueous phospholipid monolayer has important implications for the potential uses of these solvents and for our understanding of how biomolecules behave in the absence of water., Comment: Electronic Supplementary Information (ESI) available: All analysis/plotting scripts and figures files, allowing for a fully reproducible, and automated, analysis workflow for the work presented is available at https://github.com/arm61/lipids_at_airdes (DOI: 10.5281/zenodo.2577796) under a CC-BY-SA 4.0 license

Solid electrolytes for solid-state Li-ion batteries are stimulating considerable interest for next-generation energy storage applications. The Li$_7$La$_3$Zr$_2$O$_{12}$ garnet-type solid electrolyte has received appreciable attention as a result of its high ionic conductivity. However, several challenges for the successful application of solid-state devices based on Li$_7$La$_3$Zr$_2$O$_{12}$ remain, such as dendrite formation and maintaining physical contact at interfaces over many Li intercalation/extraction cycles. Here, we apply first-principles density functional theory to provide insights into the Li$_7$La$_3$Zr$_2$O$_{12}$ particle morphology under various physical and chemical conditions. Our findings indicate Li segregation at the surfaces, suggesting Li-rich grain boundaries at typical synthesis and sintering conditions. On the basis of our results, we propose practical strategies to curb Li segregation at the Li$_7$La$_3$Zr$_2$O$_{12}$ interfaces. This approach can be extended to other Li-ion conductors for the design of practical energy storage devices.

DL_MONTE is an open source, general-purpose software package for performing Monte Carlo simulations. It includes a wide variety of force fields and MC techniques, and thus is applicable to a broad range of problems in molecular simulation. Here we provide an overview of DL_MONTE, focusing on key features recently added to the package. These include the ability to treat systems confined to a planar pore (i.e. `slit' or `slab' boundary conditions); the lattice-switch Monte Carlo (LSMC) method for evaluating precise free energy differences between competing polymorphs; various commonly-used methods for evaluating free energy profiles along transition pathways (including umbrella sampling, Wang-Landau and transition matrix); and a supplementary Python toolkit for simulation management and application of the histogram reweighting analysis method. We provide two `real world' examples to elucidate the use of these methods in DL_MONTE. In particular, we apply umbrella sampling to calculate the free energy profile associated with the translocation of a lipid through a bilayer. Moreover we employ LSMC to examine the thermodynamic stability of two plastic crystal phases of water at high pressure. Beyond this, we provide instructions on how to access DL_MONTE, and point to additional information valuable to existing and prospective users.

The layered semiconductor SnSe is one of the highest-performing thermoelectric materials known. We demonstrate, through a first-principles lattice-dynamics study, that the high-temperature Cmcm phase is a dynamic average over lower-symmetry minima separated by very small energetic barriers. Compared to the low-temperature Pnma phase, the Cmcm phase displays a phonon softening and enhanced three-phonon scattering, leading to an anharmonic damping of the low-frequency modes and hence the thermal transport. We develop a renormalisation scheme to quantify the effect of the soft modes on the calculated properties, and confirm that the anharmonicity is an inherent feature of the Cmcm phase. These results suggest a design concept for thermal insulators and thermoelectric materials, based on displacive instabilities, and highlight the power of lattice-dynamics calculations for materials characterization., Comment: Merged article + supporting information

The lead chalcogenides represent an important family of functional materials, in particular due to the benchmark high-temperature thermoelectric performance of PbTe. A number of recent investigations, experimental and theoretical, have aimed to gather insight into their unique lattice dynamics and electronic structure. However, the majority of first-principles modelling has been performed at fixed temperatures, and there has been no comprehensive and systematic computational study of the effect of temperature on the material properties. We report a comparative lattice-dynamics study of the temperature dependence of the properties of PbS, PbSe and PbTe, focussing particularly on those relevant to thermoelectric performance, viz. phonon frequencies, lattice thermal conductivity, and electronic band structure. Calculations are performed within the quasi-harmonic approximation, with the inclusion of phonon-phonon interactions from many-body perturbation theory, which are used to compute phonon lifetimes and predict the lattice thermal conductivity. The results are critically compared against experimental data and other calculations, and add new insight to on-going research on the PbX compounds in relation to the off-centring of Pb at high temperatures, which is shown to be related to phonon softening. The agreement with experiment suggests that this method could serve as a straightforward, powerful and generally-applicable means of investigating the temperature dependence of material properties from first principles., Comment: Article (19 pages, 7 figures) and supporting information