75 results found
Skylaris C-K, Haynes PD, Mostofi AA, et al., 2020, Recent progress in linear-scaling density functional calculations with plane waves and pseudopotentials: the ONETEP code (vol 20, 064209, 2008), JOURNAL OF PHYSICS-CONDENSED MATTER, Vol: 32, ISSN: 0953-8984
Skylaris C-K, Haynes PD, Mostofi AA, et al., 2020, Using ONETEP for accurate and efficient O(N) density functional calculations (vol 17, 175757, 2005), JOURNAL OF PHYSICS-CONDENSED MATTER, Vol: 32, ISSN: 0953-8984
Haynes PD, Skylaris C-K, Mostofi AA, et al., 2020, Density kernel optimization in the ONETEP code (vol 20, 294207, 2008), JOURNAL OF PHYSICS-CONDENSED MATTER, Vol: 32, ISSN: 0953-8984
Oliveira MJT, Papior N, Pouillon Y, et al., 2020, The CECAM Electronic Structure Library and the modular software development paradigm, Journal of Chemical Physics, Vol: 153, Pages: 024117-1-024117-23, ISSN: 0021-9606
First-principles electronic structure calculations are very widely usedthanks to the many successful software packages available. Their traditionalcoding paradigm is monolithic, i.e., regardless of how modular its internalstructure may be, the code is built independently from others, from thecompiler up, with the exception of linear-algebra and message-passinglibraries. This model has been quite successful for decades. The rapid progressin methodology, however, has resulted in an ever increasing complexity of thoseprograms, which implies a growing amount of replication in coding and in therecurrent re-engineering needed to adapt to evolving hardware architecture. TheElectronic Structure Library (\esl) was initiated by CECAM (European Centre forAtomic and Molecular Calculations) to catalyze a paradigm shift away from themonolithic model and promote modularization, with the ambition to extractcommon tasks from electronic structure programs and redesign them as free,open-source libraries. They include ``heavy-duty'' ones with a high degree ofparallelisation, and potential for adaptation to novel hardware within them,thereby separating the sophisticated computer science aspects of performanceoptimization and re-engineering from the computational science done byscientists when implementing new ideas. It is a community effort, undertaken bydevelopers of various successful codes, now facing the challenges arising inthe new model. This modular paradigm will improve overall coding efficiency andenable specialists (computer scientists or computational scientists) to usetheir skills more effectively. It will lead to a more sustainable and dynamicevolution of software as well as lower barriers to entry for new developers.
Pomiro F, Ablitt C, Bristowe NC, et al., 2020, From first- to second-order phase transitions in hybrid improper ferroelectrics through entropy stabilization, Physical Review B, Vol: 102, Pages: 014101 – 1-014101 – 8, ISSN: 2469-9950
Hybrid improper ferroelectrics (HIFs) have been studied intensively over the past few years to gain an understanding of their temperature-induced phase transitions and ferroelectric switching pathways. Here we report a switching from a first- to a second-order phase transition pathway for HIFs Ca3−xSrxTi2O7, which is driven by the differing entropies of the phases that we identify as being associated with the dynamic motion of octahedral tilts and rotations. A greater understanding of the transition pathways in this class of layered perovskites, which host many physical properties that are coupled to specific symmetries and octahedral rotation and tilt distortions—such as superconductivity, negative thermal expansion, fast ion conductivity, ferroelectricity, among others—is a crucial step in creating novel functional materials by design.
Goodwin Z, Vitale V, Liang X, et al., 2020, Hartree theory calculations of quasiparticle properties in twisted bilayer graphene, Physical Review B: Condensed Matter and Materials Physics, ISSN: 1098-0121
A detailed understanding of interacting electrons in twisted bilayer graphene(tBLG) near the magic angle is required to gain insights into the physicalorigin of the observed broken symmetry phases including correlated insulatorstates and superconductivity. Here, we present extensive atomistic Hartreetheory calculations of the electronic properties of tBLG in the (semi-)metallicphase as function of doping and twist angle. Specifically, we calculatequasiparticle properties, such as the band structure, density of states (DOS)and local density of states (LDOS), which are directly accessible inphotoemission and tunnelling spectroscopy experiments. We find thatquasiparticle properties change significantly upon doping - an effect which isnot captured by tight-binding theory. In particular, we observe that thepartially occupied bands flatten significantly which enhances the density ofstates at the Fermi level and explains the experimentally observed Fermi levelpinning. We predict a clear signature of this band flattening in the LDOS inthe AB/BA regions of tBLG which can be tested in scanning tunnelingexperiments. We also study the dependence of quasiparticle properties on thedielectric environment of tBLG and discover that these properties aresurprisingly robust as a consequence of the strong internal screening. Finally,we present a simple analytical expression for the Hartree potential whichenables the determination of quasiparticle properties without the need forself-consistent calculations.
Gołębiowski JR, Kermode JR, Haynes PD, et al., 2020, Correction: Atomistic QM/MM simulations of the strength of covalent interfaces in carbon nanotube-polymer composites., Physical Chemistry Chemical Physics, Vol: 22, Pages: 14375-14375, ISSN: 1463-9076
Correction for 'Atomistic QM/MM simulations of the strength of covalent interfaces in carbon nanotube-polymer composites' by Jacek R. Gołębiowski et al., Phys. Chem. Chem. Phys., 2020, 22, 12007-12014, DOI: 10.1039/d0cp01841d.
Maximally-localised Wannier functions (MLWFs) are routinely used to compute from first-principles advanced materials properties that require very dense Brillouin zone integration and to build accurate tight-binding models for scale-bridging simulations. At the same time, high-throughput (HT) computational materials design is an emergent field that promises to accelerate reliable and cost-effective design and optimisation of new materials with target properties. The use of MLWFs in HT workflows has been hampered by the fact that generating MLWFs automatically and robustly without any user intervention and for arbitrary materials is, in general, very challenging. We address this problem directly by proposing a procedure for automatically generating MLWFs for HT frameworks. Our approach is based on the selected columns of the density matrix method and we present the details of its implementation in an AiiDA workflow. We apply our approach to a dataset of 200 bulk crystalline materials that span a wide structural and chemical space. We assess the quality of our MLWFs in terms of the accuracy of the band-structure interpolation that they provide as compared to the band-structure obtained via full first-principles calculations. Finally, we provide a downloadable virtual machine that can be used to reproduce the results of this paper, including all first-principles and atomistic simulations as well as the computational workflows.
Prentice J, Aarons J, Womack JC, et al., 2020, The ONETEP linear-scaling density functional theory program, The Journal of Chemical Physics, Vol: 152, Pages: 174111-1-174111-36, ISSN: 0021-9606
We present an overview of the onetep program for linear-scaling density functional theory (DFT) calculations with large basis set (plane-wave) accuracy on parallel computers. The DFT energy is computed from the density matrix, which is constructed from spatially localized orbitals we call Non-orthogonal Generalized Wannier Functions (NGWFs), expressed in terms of periodic sinc (psinc) functions. During the calculation, both the density matrix and the NGWFs are optimized with localization constraints. By taking advantage of localization, onetep is able to perform calculations including thousands of atoms with computational effort, which scales linearly with the number or atoms. The code has a large and diverse range of capabilities, explored in this paper, including different boundary conditions, various exchange–correlation functionals (with and without exact exchange), finite electronic temperature methods for metallic systems, methods for strongly correlated systems, molecular dynamics, vibrational calculations, time-dependent DFT, electronic transport, core loss spectroscopy, implicit solvation, quantum mechanical (QM)/molecular mechanical and QM-in-QM embedding, density of states calculations, distributed multipole analysis, and methods for partitioning charges and interactions between fragments. Calculations with onetep provide unique insights into large and complex systems that require an accurate atomic-level description, ranging from biomolecular to chemical, to materials, and to physical problems, as we show with a small selection of illustrative examples. onetep has always aimed to be at the cutting edge of method and software developments, and it serves as a platform for developing new methods of electronic structure simulation. We therefore conclude by describing some of the challenges and directions for its future developments and applications.
Golebiowski J, Kermode J, Haynes P, et al., 2020, Atomistic QM/MM simulations of the strength of covalent interfaces in carbon nanotube–polymer composites, Physical Chemistry Chemical Physics, Vol: 22, Pages: 12007-12014, ISSN: 1463-9076
We investigate the failure of carbon-nanotube/polymer composites by using a recently-developed hybrid quantum-mechanical/molecular-mechanical (QM/MM) approach to simulate nanotube pull-out from a cross-linked polyethene matrix. Our study focuses on the strength and failure modes of covalently-bonded nanotube–polymer interfaces based on amine, carbene and carboxyl functional groups and a [2+1] cycloaddition. We find that the choice of the functional group linking the polymer matrix to the nanotube determines the effective strength of the interface, which can be increased by up to 50% (up to the limit dictated by the strength of the polymer backbone itself) by choosing groups with higher interfacial binding energy. We rank the functional groups presented in this work based on the strength of the resulting interface and suggest broad guidelines for the rational design of nanotube functionalisation for nanotube–polymer composites.
Goodwin Z, Vitale V, Corsetti F, et al., 2020, Critical role of device geometry for the phase diagram of twisted bilayer graphene, Physical Review B: Condensed Matter and Materials Physics, Vol: 101, Pages: 1-8, ISSN: 1098-0121
The effective interaction between electrons in two-dimensional materials can be modified by their environment, enabling control of electronic correlations and phases. Here, we study the dependence of electronic correlations in twisted bilayer graphene (tBLG) on the separation to the metallic gate(s) in two device configurations. Using an atomistic tight-binding model, we determine the Hubbard parameters of the flat bands as a function of gate separation, taking into account the screening from the metallic gate(s), the dielectric spacer layers, and the tBLG itself. We determine the critical gate separation at which the Hubbard parameters become smaller than the critical value required for a transition from a correlated insulator state to a (semi)metallic phase. We show how this critical gate separation depends on twist angle, doping, and the device configuration. These calculations may help rationalize the reported differences between recent measurements of tBLG's phase diagram and suggest that correlated insulator states can be screened out in devices with thin dielectric layers.
Aghajanian M, Schuler B, Cochrane KA, et al., 2020, Resonant and bound states of charged defects in two-dimensional semiconductors, Physical Review B: Condensed Matter and Materials Physics, Vol: 101, Pages: 1-6, ISSN: 1098-0121
A detailed understanding of charged defects in two-dimensional semiconductors is needed for the development of ultrathin electronic devices. Here, we study negatively charged acceptor impurities in monolayer WS2 using a combination of scanning tunneling spectroscopy and large-scale atomistic electronic structure calculations. We observe several localized defect states of hydrogenic wave function character in the vicinity of the valence band edge. Some of these defect states are bound, while others are resonant. The resonant states result from the multivalley valence band structure of WS2, whereby localized states originating from the secondary valence band maximum at Γ hybridize with continuum states from the primary valence band maximum at K/K′. Resonant states have important consequences for electron transport as they can trap mobile carriers for several tens of picoseconds.
Pizzi G, Vitale V, Arita R, et al., 2020, Wannier90 as a community code: new features and applications, Journal of Physics: Condensed Matter, Vol: 32, Pages: 1-25, ISSN: 0953-8984
Wannier90 is an open-source computer program for calculating maximally-localised Wannier functions (MLWFs) from a set of Bloch states. It is interfaced to many widely used electronic-structure codes thanks to its independence from the basis sets representing these Bloch states. In the past few years the development of Wannier90 has transitioned to a community-driven model; this has resulted in a number of new developments that have been recently released in Wannier90 v3.0. In this article we describe these new functionalities, that include the implementation of new features for wannierisation and disentanglement (symmetry-adapted Wannier functions, selectively-localised Wannier functions, selected columns of the density matrix) and the ability to calculate new properties (shift currents and Berry-curvature dipole, and a new interface to many-body perturbation theory); performance improvements, including parallelisation of the core code; enhancements in functionality (support for spinor-valued Wannier functions, more accurate methods to interpolate quantities in the Brillouin zone); improved usability (improved plotting routines, integration with high-throughput automation frameworks), as well as the implementation of modern software engineering practices (unit testing, continuous integration, and automatic source-code documentation). These new features, capabilities, and code development model aim to further sustain and expand the community uptake and range of applicability, that nowadays spans complex and accurate dielectric, electronic, magnetic, optical, topological and transport properties of materials.
Ablitt C, McCay H, Craddock S, et al., 2019, Tolerance factor control of uniaxial negative thermal expansion in a layered perovskite, Chemistry of Materials, Vol: 32, Pages: 605-610, ISSN: 0897-4756
By tuning the tolerance factor, $t$, of the Ruddlesden--Popper oxide Ca$_2$MnO$_4$ through isovalent substitutions we show that the uniaxial coefficient of linear thermal expansion (CLTE) of these systems can be systematically changed through large negative to positive values. High-resolution X-ray diffraction measurements show that the magnitude of uniaxial negative thermal expansion (NTE) increases as $t$ decreases across the stability window of the NTE phase. Transitions to phases with positive thermal expansion (PTE) are found to occur at both the high-$t$ and low-$t$ limits of stability. First-principles calculations demonstrate that reducing $t$ enhances the contribution to thermal expansion from the lowest frequency phonons, which have the character of octahedral tilts and have negative mode Gr\"uneisen parameter components along the NTE axis. By tuning $t$ to the lower edge of the NTE phase stability window, we are hence able to maximise the amplitudes of these vibrations and thereby maximise NTE with a CLTE of -8.1~ppm/K at 125~K. We also illustrate, at the other end of the phase diagram, that an enhancement in compliance of these materials associated with the rotational instability provides another mechanism by which NTE could be yet further enhanced in this and related systems.
Goodwin Z, Corsetti F, Mostofi A, et al., 2019, Attractive electron-electron interactions from internal screening in magic angle twisted bilayer graphene, Physical Review B: Condensed Matter and Materials Physics, Vol: 100, ISSN: 1098-0121
Twisted bilayer graphene (tBLG) has recently emerged as a new platform for studying electroncorrelations, the strength of which can be controlled via the twist angle. Here, we study the effectof internal screening on electron-electron interactions in undoped tBLG. Using the random phaseapproximation, we find that the dielectric response of tBLG drastically increases near the magicangle and is highly twist-angle dependent. As a consequence of the abrupt change of the Fermivelocity as a function of wave vector, the screened interaction in real space exhibits attractiveregions for certain twist angles near the magic angle. Attractive interactions can induce chargedensity waves and superconductivity and therefore our findings could be relevant to understand themicroscopic origins of the recently observed strong correlation phenomena in undoped tBLG. Theresulting screened Hubbard parameters are strongly reduced and exhibit a non-linear dependence onthe twist angle. We also carry out calculations with the constrained random phase approximationand parametrize a twist-angle dependent Keldysh model for the resulting effective interaction.
Prentice J, Charlton R, Mostofi AA, et al., 2019, Combining embedded mean-field theory with linear-scaling density-functional theory, Journal of Chemical Theory and Computation, Vol: 16, Pages: 354-365, ISSN: 1549-9618
We demonstrate the capability of embedded mean field theory (EMFT) within the linear-scaling density-functional theory code ONETEP, which enables DFT-in-DFT quantum embedding calculations on systems containing thousands of atoms at a fraction of the cost of a full calculation. We perform simulations on a wide range of systems from molecules to complex nanostructures to demonstrate the performance of our implementation with respect to accuracy and efficiency. This work paves the way for the application of this class of quantum embedding method to large-scale systems that are beyond the reach of existing implementations.
Goodwin ZAH, Corsetti F, Mostofi AA, et al., 2019, Twist-angle sensitivity of electron correlations in moiré graphene bilayers, Physical Review B, Vol: 100, ISSN: 2469-9950
Motivated by the recent observation of correlated insulator states and unconventional superconductivity in twisted bilayer graphene, we study the dependence of electron correlations on the twist angle and reveal the existence of strong correlations over a narrow range of twist angles near the magic angle. Specifically, we determine the on-site and extended Hubbard parameters of the low-energy Wannier states using an atomistic quantum-mechanical approach. The ratio of the on-site Hubbard parameter and the width of the flat bands, which is an indicator of the strength of electron correlations, depends sensitively on the screening by the semiconducting substrate and the metallic gates. Including the effect of long-ranged Coulomb interactions significantly reduces electron correlations and explains the experimentally observed sensitivity of strong-correlation phenomena on twist angles.
Mostofi A, Ablitt C, Bristowe N, et al., 2019, Negative thermal expansion in high pressure layered perovskite Ca2GeO4, Chemical Communications, Vol: 55, Pages: 2984-2987, ISSN: 1359-7345
We report the high pressure synthesis of a layered perovskite Ca2GeO4 which is found to have the Ruddlesden–Popper structure with I41/acd symmetry. Consonant with our recent predictions [Ablitt et al., npj Comput. Mater., 2017, 3, 44], the phase displays pronounced uniaxial negative thermal expansion over a large temperature range. Negative thermal expansion that persists over a large temperature range is very unusual in the perovskite structure, and its occurrence in this instance can be understood to arise due to both soft lattice vibrations associated with a phase competition and the unusually compliant nature of this structure, which effectively couples thermal expansion in the layer plane to lattice contractions perpendicular to the layering direction via a “corkscrew” mechanism.
Golebiowski J, Kermode J, Mostofi A, et al., 2018, Multiscale simulations of critical interfacial failure in carbon nanotube-polymer composites, Journal of Chemical Physics, Vol: 149, ISSN: 0021-9606
Computational investigation of interfacial failure in composite materials is challenging because it is inherently multi-scale: the bond-breaking processes that occur at the covalently bonded interface and initiate failure involve quantum mechanical phenomena, yet the mechanisms by which external stresses are transferred through the matrix occur on length and time scales far in excess of anything that can be simulated quantum mechanically. In this work, we demonstrate and validate an adaptive quantum mechanics (QM)/molecular mechanics simulation method that can be used to address these issues and apply it to study critical failure at a covalently bonded carbon nanotube (CNT)-polymer interface. In this hybrid approach, the majority of the system is simulated with a classical forcefield, while areas of particular interest are identified on-the-fly and atomic forces in those regions are updated based on QM calculations. We demonstrate that the hybrid method results are in excellent agreement with fully QM benchmark simulations and offers qualitative insights missing from classical simulations. We use the hybrid approach to show how the chemical structure at the CNT-polymer interface determines its strength, and we propose candidate chemistries to guide further experimental work in this area.
Mostofi AA, Ablitt C, Senn M, et al., 2018, Control of uniaxial negative thermal expansion in layered Perovskites by tuning layer thickness, Frontiers in Chemistry, Vol: 6, ISSN: 2296-2646
Uniaxial negative thermal expansion (NTE) is known to occur in low n members of the An+1BnO3n+1 Ruddlesden–Popper (RP) layered perovskite series with a frozen rotation of BO6 octahedra about the layering axis. Previous work has shown that this NTE arises due to the combined effects of a close proximity to a transition to a competing phase, so called “symmetry trapping”, and highly anisotropic elastic compliance specific to the symmetry of the NTE phase. We extend this analysis to the broader RP family (n = 1, 2, 3, 4, …, ∞), demonstrating that by changing the fraction of layer interface in the structure (i.e., the value of 1/n) one may control the anisotropic compliance that is necessary for the pronounced uniaxial NTE observed in these systems. More detailed analysis of how the components of the compliance matrix develop with 1/n allows us to identify different regimes, linking enhancements in compliance between these regimes to the crystallographic degrees of freedom in the structure. We further discuss how the perovskite layer thickness affects the frequencies of soft zone boundary modes with large negative Grüneisen parameters, associated with the aforementioned phase transition, that constitute the thermodynamic driving force for NTE. This new insight complements our previous work—showing that chemical control may be used to switch from positive to negative thermal expansion in these systems—since it makes the layer thickness, n, an additional design parameter that may be used to engineer layered perovskites with tuneable thermal expansion. In these respects, we predict that, with appropriate chemical substitution, the n = 1 phase will be the system in which the most pronounced NTE could be achieved.
Wong D, Wang Y, Jin W, et al., 2018, Microscopy of hydrogen and hydrogen-vacancy defect structures on graphene devices, Physical review B: Condensed matter and materials physics, Vol: 98, ISSN: 1098-0121
We have used scanning tunneling microscopy (STM) to investigate two types of hydrogen defect structures on monolayer graphene supported by hexagonal boron nitride (h−BN) in a gated field-effect transistor configuration. The first H-defect type is created by bombarding graphene with 1-keV ionized hydrogen and is identified as two hydrogen atoms bonded to a graphene vacancy via comparison of experimental data to first-principles calculations. The second type of H defect is identified as dimerized hydrogen and is created by depositing atomic hydrogen having only thermal energy onto a graphene surface. Scanning tunneling spectroscopy (STS) measurements reveal that hydrogen dimers formed in this way open a new elastic channel in the tunneling conductance between an STM tip and graphene.
Molinari N, Sutton A, Mostofi AA, 2018, Mechanisms of reinforcement in polymer nanocomposites, Physical Chemistry Chemical Physics, Vol: 20, Pages: 23085-23094, ISSN: 1463-9076
Coarse-grained molecular dynamics simulations are used to elucidate molecular mechanisms responsible for different mechanical behaviours of elastomers containing spherical particles with different volume fractions. We observe that different filler volume fractions result in qualitatively different responses of the polymer nanocomposite to tensile strain. At relatively low filler volume fraction a yield drop appears in the stress–strain curve. As the filler volume fraction increases there is a reduction in the rate of plastic hardening, becoming plastic softening at sufficiently high filler volume fraction. We demonstrate that these behaviours are a result of the network formed by the polymer chains and filler particles. We identify three distinct molecular structural motifs between polymer and filler particles whose relative prevalence varies with the filler volume fraction and as the system is dynamically strained. We show how this evolution in molecular structure is directly linked to the observed mechanical response.
Lischner JC, Mostofi AA, Aghajanian M, 2018, Tuning electronic properties of transition-metal dichalcogenides via defect charge, Scientific Reports, Vol: 8, ISSN: 2045-2322
Defect engineering is a promising route for controlling the electronic properties of monolayer transition-metal dichalcogenide (TMD) materials. Here, we demonstrate that the electronic structure of MoS2 depends sensitively on the defect charge, both its sign and magnitude. In particular, we study shallow bound states induced by charged defects using large-scale tight-binding simulations with screened defect potentials and observe qualitative changes in the orbital character of the lowest lying impurity states as function of the impurity charge. To gain further insights, we analyze the competition of impurity states originating from different valleys of the TMD band structure using effective mass theory and find that impurity state binding energies are controlled by the effective mass of the corresponding valley, but with significant deviations from hydrogenic behaviour due to unconventional screening of the defect potential.
Ablitt C, Craddock S, Senn MS, et al., 2017, The origin of uniaxial negative thermal expansion in layered perovskites, npj Computational Materials, Vol: 3, ISSN: 2057-3960
Why is it that ABO3 perovskites generally do not exhibit negative thermal expansion (NTE) over a wide temperature range, whereas layered perovskites of the same chemical family often do? It is generally accepted that there are two key ingredients that determine the extent of NTE: the presence of soft phonon modes that drive contraction (have negative Grüneisen parameters); and anisotropic elastic compliance that predisposes the material to the deformations required for NTE along a specific axis. This difference in thermal expansion properties is surprising since both ABO3 and layered perovskites often possess these ingredients in equal measure in their high-symmetry phases. Using first principles calculations and symmetry analysis, we show that in layered perovskites there is a significant enhancement of elastic anisotropy due to symmetry breaking that results from the combined effect of layering and condensed rotations of oxygen octahedra. This feature, unique to layered perovskites of certain symmetry, is what allows uniaxial NTE to persist over a large temperature range. This fundamental insight means that symmetry and the elastic tensor can be used as descriptors in high-throughput screening and to direct materials design.
Wong D, Corsetti F, Wang Y, et al., 2017, Spatially resolving density-dependent screening around a single charged atom in graphene, Physical Review B, Vol: 95, ISSN: 2469-9950
Electrons in two-dimensional graphene sheets behave as interacting chiral Dirac fermions and have unique screening properties due to their symmetry and reduced dimensionality. By using a combination of scanning tunneling spectroscopy measurements and theoretical modeling we have characterized how graphene's massless charge carriers screen individual charged calcium atoms. A backgated graphene device configuration has allowed us to directly visualize how the screening length for this system can be tuned with carrier density. Our results provide insight into electron-impurity and electron-electron interactions in a relativistic setting with important consequences for other graphene-based electronic devices.
Corsetti F, Mostofi AA, Lischner JL, 2017, First-principles multiscale modelling of charged adsorbates on doped graphene, 2D Materials, Vol: 4, ISSN: 2053-1583
Adsorbed atoms and molecules play an important role in controlling and tuning the functional properties of two-dimensional (2D) materials. Understanding and predicting this process from theory is challenging because of the need to capture the complex interplay between the local chemistry and the long-range screening response. To address this problem, we present a first-principles multiscale approach that combines linear-scaling density-functional theory, continuum screening theory and large-scale tight-binding simulations into a seamless parameter-free theory of adsorbates on 2D materials. We apply this method to investigate the electronic structure of doped graphene with a single calcium (Ca) adatom and find that the Ca atom acts as a Coulomb impurity which modifies the graphene local density of states (LDOS) within a distance of several nanometres in its vicinity. We also observe an important doping dependence of the graphene LDOS near the Ca atom, which gives insights into electronic screening in graphene. Our multiscale framework opens up the possibility of investigating complex mesoscale adsorbate configurations on 2D materials relevant to real devices.
Khawaja M, Sutton AP, Mostofi AA, 2017, Molecular Simulation of Gas Solubility in Nitrile Butadiene Rubber., J Phys Chem B, Vol: 121, Pages: 287-297
Molecular simulation is used to compute the solubility of small gases in nitrile butadiene rubber (NBR) with a Widom particle-insertion technique biased by local free volume. The convergence of the method is examined as a function of the number of snapshots upon which the insertions are performed and the number of insertions per snapshot and is compared to the convergence of the unbiased Widom insertion technique. The effect of varying the definition of local free volume is also investigated. The acrylonitrile content of the polymer is altered to examine its influence on the solubility of helium, CO2, and H2O, and the solubilities of polar gases are found to be enhanced relative to those of nonpolar gases, in qualitative agreement with experiment. To probe this phenomenon further, the solubilities are decomposed into contributions from the neighborhoods of different atoms, using a Voronoi cell construction, and a strong bias is found for CO2 and H2O in particular to be situated near nitrogen sites in the elastomer. Temperature is shown to suppress the solubility of CO2 and H2O but to increase that of helium. Increasing pressure is found to suppress the solubility of all gases but at different rates, according to a balance between their molecular sizes and electrostatic interactions with the polymer. These results are relevant to the use of NBR seals at elevated temperatures and pressures, such as in oil and gas wells.
Molinari N, Khawaja M, Sutton AP, et al., 2016, Molecular Model for HNBR with Tunable Cross-Link Density, The Journal of Physical Chemistry B, Vol: 120, Pages: 12700-12707, ISSN: 1520-6106
Muscatello J, Muller EA, Mostofi AA, et al., 2016, Multiscale molecular simulations of the formation and structure of polyamide membranes created by interfacial polymerization, Journal of Membrane Science, Vol: 527, Pages: 180-190, ISSN: 0376-7388
Large scale molecular simulations to model the formation of polyamide membranes have been carried out using a procedure that mimics experimental interfacial polymerization of trimesoyl chloride (TMC) and metaphenylene diamine (MPD) monomers. A coarse-grained representation of the monomers has been developed to facilitate these simulations, which captures essential features of the stereochemistry of the monomers and of amide bonding between them. Atomic models of the membranes are recreated from the final coarse-grained representations. Consistent with earlier treatments, membranes are formed through the growth and aggregation of oligomer clusters. The membranes are inhomogeneous, displaying opposing gradients of trapped carboxyl and amine side groups, local density variations, and regions where the density of amide bonding is reduced as a result of the aggregation process. We observe the interfacial polymerization reaction is self-limiting and the simulated membranes display a thickness of 5–10 nm. They also display a surface roughness of 1–4 nm. Comparisons are made with recently published experimental results on the structure and chemistry of these membranes and some interesting similarities and differences are found.
Elliott JD, Poli E, Scivetti I, et al., 2016, Chemically selective alternatives to photoferroelectrics for polarization-enhanced photocatalysis: the untapped potential of hybrid inorganic nanotubes, Advanced Science, Vol: 4, ISSN: 2198-3844
Linear-scaling density functional theory simulation of methylated imogolite nanotubes (NTs) elucidates the interplay between wall-polarization, bands separation, charge-transfer excitation, and tunable electrostatics inside and outside the NT-cavity. The results suggest that integration of polarization-enhanced selective photocatalysis and chemical separation into one overall dipole-free material should be possible. Strategies are proposed to increase the NT polarization for maximally enhanced electron–hole separation.
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