Institut de minéralogie, de physique des matériaux et de cosmochimie

QUANTUM ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). The acronym ESPRESSO stands for opEn Source Package for Research in Electronic Structure, Simulation, and Optimization. It is freely available to researchers around the world under the terms of the GNU General Public License. QUANTUM ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively parallel architectures, and a great effort being devoted to user friendliness. QUANTUM ESPRESSO is evolving towards a distribution of independent and interoperable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.

Graphene is the two-dimensional building block for carbon allotropes of every other dimensionality. We show that its electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers. The D peak second order changes in shape, width, and position for an increasing number of layers, reflecting the change in the electron bands via a double resonant Raman process. The G peak slightly down-shifts. This allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area.

Quantum EXPRESSO is an integrated suite of open-source computer codes for quantum simulations of materials using state-of-the-art electronic-structure techniques, based on density-functional theory, density-functional perturbation theory, and many-body perturbation theory, within the plane-wave pseudopotential and projector-augmented-wave approaches. Quantum EXPRESSO owes its popularity to the wide variety of properties and processes it allows to simulate, to its performance on an increasingly broad array of hardware architectures, and to a community of researchers that rely on its capabilities as a core open-source development platform to implement their ideas. In this paper we describe recent extensions and improvements, covering new methodologies and property calculators, improved parallelization, code modularization, and extended interoperability both within the distribution and with external software.

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.

The widespread popularity of density functional theory has given rise to an extensive range of dedicated codes for predicting molecular and crystalline properties. However, each code implements the formalism in a different way, raising questions about the reproducibility of such predictions. We report the results of a community-wide effort that compared 15 solid-state codes, using 40 different potentials or basis set types, to assess the quality of the Perdew-Burke-Ernzerhof equations of state for 71 elemental crystals. We conclude that predictions from recent codes and pseudopotentials agree very well, with pairwise differences that are comparable to those between different high-precision experiments. Older methods, however, have less precise agreement. Our benchmark provides a framework for users and developers to document the precision of new applications and methodological improvements.

International audience

Quantum ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). Quantum ESPRESSO stands for "opEn Source Package for Research in Electronic Structure, Simulation, and Optimization". It is freely available to researchers around the world under the terms of the GNU General Public License. Quantum ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively-parallel architectures, and a great effort being devoted to user friendliness. Quantum ESPRESSO is evolving towards a distribution of independent and inter-operable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.

We present a scheme for the calculation of magnetic response parameters in insulators using ultrasoft pseudopotentials. It uses the gauge-including projector augmented wave method [C. J. Pickard and F. Mauri, Phys. Rev. B 63, 245101 (2001)] to obtain all-electron accuracy for both finite and infinitely periodic systems. We consider in detail the calculation of NMR chemical shieldings. The approach is successfully validated first for molecular systems by comparing calculated chemical shieldings for a range of molecules with quantum chemistry results and then in the solid state by comparing $^{17}\mathrm{O}$ NMR parameters calculated for silicates with experiment.

Na2Ti3O7 is found to reversibly uptake 2 Na ions per formula unit (200 mA h/g) at an average potential of 0.3 V and is hence a very promising negative electrode material for building sodium ion batteries working at room temperature.

In environmental magnetism, rock and mineral magnetic techniques are used to investigate the formation, transportation, deposition, and postdepositional alterations of magnetic minerals under the influences of a wide range of environmental processes. All materials respond in some way to an applied magnetic field, and iron‐bearing minerals are sensitive to a range of environmental processes, which makes magnetic measurements extremely useful for detecting signals associated with environmental processes. Environmental magnetism has grown considerably since the mid 1970s and now contributes to research in the geosciences and in branches of physics, chemistry, and biology and environmental science, including research on climate change, pollution, iron biomineralization, and depositional and diagenetic processes in sediments to name a few applications. Magnetic parameters are used to routinely scan sediments, but interpretation is often difficult and requires understanding of the underlying physics and chemistry. Thorough examination of magnetic properties and of the environmental processes that give rise to the measured magnetic signal is needed to avoid ambiguities, complexities, and limitations to interpretations. In this review, we evaluate environmental magnetic parameters based on theory and empirical results. We describe how ambiguities can be resolved by use of combined techniques and demonstrate the power of environmental magnetism in enabling quantitative environmental interpretations. We also review recent developments that demonstrate the mutual benefit of environmental magnetism from close collaborations with biology, chemistry, and physics. Finally, we discuss directions in which environmental magnetism is likely to develop in the future.

Electronic structure Density-functional theory Many-body perturbation theory Abinit 2009 publication. Links with several other computational materials science projects are described. This article also covers the new capabilities of Abinit that have been implemented during the last three years, complementing a recent update of the 2009

In their late stages of evolution, peraluminous granitic melts exsolve large amounts of fluids which can modify the chemical composition of granitic whole-rock samples. The niobium/tantalum (Nb/Ta) ratio is expected to decrease during the magmatic differentiation of granitic melts, but the behavior of both elements at the magmatic-hydrothermal transition remains unclear. Using a compilation of whole-rock geochemical data available in the literature, we demonstrate that fractional crystallization alone is not sufficient to explain the distribution of Nb-Ta in most peraluminous granites. However, we notice that most of the granitic samples displaying evidence of interactions with fluids have Nb/Ta < 5. We propose that the decrease of the Nb/Ta ratio in evolved melts is the consequence of both fractional crystallization and sub-solidus hydrothermal alteration. We suggest that the Nb/Ta value of ~5 fingerprints the magmatic-hydrothermal transition in peraluminous granites. Furthermore, a Nb/Ta ratio of ~5 appears to be a good marker to discriminate mineralized from barren peraluminous granites.

We determine the stability, the geometry, the electronic, and magnetic structure of hydrogen-terminated graphene-nanoribbon edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely low ultravacuum pressures. Under more standard conditions, the most stable structures are the mono- and dihydrogenated armchair edges and a zigzag edge reconstruction with one di- and two monohydrogenated sites. At high hydrogen concentration "bulk" graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule).

Earth's core is structured in a solid inner core, mainly composed of iron, and a liquid outer core. The temperature at the inner core boundary is expected to be close to the melting point of iron at 330 gigapascal (GPa). Despite intensive experimental and theoretical efforts, there is little consensus on the melting behavior of iron at these extreme pressures and temperatures. We present static laser-heated diamond anvil cell experiments up to 200 GPa using synchrotron-based fast x-ray diffraction as a primary melting diagnostic. When extrapolating to higher pressures, we conclude that the melting temperature of iron at the inner core boundary is 6230 ± 500 kelvin. This estimation favors a high heat flux at the core-mantle boundary with a possible partial melting of the mantle.

We calculate the double-resonant (DR) Raman spectrum of graphene, and determine the lines associated to both phonon-defect processes (such as in the $D$ line at $\ensuremath{\sim}$1350 cm${}^{\ensuremath{-}1}$, ${D}^{\ensuremath{'}}$ at $\ensuremath{\sim}$1600 cm${}^{\ensuremath{-}1}$, and ${D}^{\ensuremath{'}\ensuremath{'}}$ at $\ensuremath{\sim}$1100 cm${}^{\ensuremath{-}1}$), and two-phonon ones (such as in the $2D$, $2{D}^{\ensuremath{'}}$, or $D+{D}^{\ensuremath{'}\ensuremath{'}}$ lines). Phonon and electronic dispersions reproduce calculations based on density-functional theory corrected with GW. Electron-light, -phonon, and -defect scattering matrix elements and the electronic linewidth are explicitly calculated. Defect-induced processes are simulated by considering different kinds of idealized defects. For an excitation energy of ${\ensuremath{\epsilon}}_{L}=2.4$ eV, the agreement with measurements is very good and calculations reproduce the relative intensities among phonon-defect or among two-phonon lines; the measured small widths of the $D$, ${D}^{\ensuremath{'}}$, $2D$, and $2{D}^{\ensuremath{'}}$ lines; the line shapes; the presence of small intensity lines in the 1800--2000-cm${}^{\ensuremath{-}1}$ range. We determine how the spectra depend on the excitation energy, on the light polarization, on the electronic linewidth, on the kind of defects, and on their concentration. According to the present findings, the intensity ratio between the $2{D}^{\ensuremath{'}}$ and $2D$ lines can be used to determine experimentally the electronic linewidth. The intensity ratio between the $D$ and ${D}^{\ensuremath{'}}$ lines depends on the kind of model defect, suggesting that this ratio could possibly be used to identify the kind of defects present in actual samples. Charged impurities outside the graphene plane provide an almost undetectable contribution to the Raman signal. The present analysis reveals that, for both $D$ and $2D$ lines, the dominant DR processes are those in which electrons and holes are both involved in the scattering, because of a destructive quantum interference that kills processes involving only electrons or only holes. The most important phonons belong to the $\mathbf{K}\ensuremath{\rightarrow}\mathbit{\ensuremath{\Gamma}}$ direction ($inner$ phonons) and not to the K $\ensuremath{\rightarrow}$ M one ($outer$ phonons), as usually assumed. The small $2D$ linewidth at ${\ensuremath{\epsilon}}_{L}=2.4$ eV is a consequence of the interplay between the opposite trigonal warpings of the electron and phonon dispersions. At higher excitation, e.g., ${\ensuremath{\epsilon}}_{L}=3.8$ eV, the $2D$ line becomes broader and evolves in an asymmetric double peak structure.

We characterize the thermal conductivity of graphite, monolayer graphene, graphane, fluorographane, and bilayer graphene, solving exactly the Boltzmann transport equation for phonons, with phonon-phonon collision rates obtained from density functional perturbation theory. For graphite, the results are found to be in excellent agreement with experiments; notably, the thermal conductivity is 1 order of magnitude larger than what found by solving the Boltzmann equation in the single mode approximation, commonly used to describe heat transport. For graphene, we point out that a meaningful value of intrinsic thermal conductivity at room temperature can be obtained only for sample sizes of the order of 1 mm, something not considered previously. This unusual requirement is because collective phonon excitations, and not single phonons, are the main heat carriers in these materials; these excitations are characterized by mean free paths of the order of hundreds of micrometers. As a result, even Fourier's law becomes questionable in typical sample sizes, because its statistical nature makes it applicable only in the thermodynamic limit to systems larger than a few mean free paths. Finally, we discuss the effects of isotopic disorder, strain, and chemical functionalization on thermal performance. Only chemical functionalization is found to play an important role, decreasing the conductivity by a factor of 2 in hydrogenated graphene, and by 1 order of magnitude in fluorogenated graphene.

Abstract It is generally believed that CO 2 electroreduction to multi‐carbon products such as ethanol or ethylene may be catalyzed with significant yield only on metallic copper surfaces, implying large ensembles of copper atoms. Here, we report on an inexpensive Cu‐N‐C material prepared via a simple pyrolytic route that exclusively feature single copper atoms with a CuN 4 coordination environment, atomically dispersed in a nitrogen‐doped conductive carbon matrix. This material achieves aqueous CO 2 electroreduction to ethanol at a Faradaic yield of 55 % under optimized conditions (electrolyte: 0.1 m CsHCO 3 , potential: −1.2 V vs. RHE and gas‐phase recycling set up), as well as CO electroreduction to C 2 ‐products (ethanol and ethylene) with a Faradaic yield of 80 %. During electrolysis the isolated sites transiently convert into metallic copper nanoparticles, as shown by operando XAS analysis, which are likely to be the catalytically active species. Remarkably, this process is reversible and the initial material is recovered intact after electrolysis.

We compute, from first principles, the frequency of the E(2g), Gamma phonon (Raman G band) of graphene, as a function of the charge doping. Calculations are done using (i) the adiabatic Born-Oppenheimer approximation and (ii) time-dependent perturbation theory to explore dynamic effects beyond this approximation. The two approaches provide very different results. While the adiabatic phonon frequency weakly depends on the doping, the dynamic one rapidly varies because of a Kohn anomaly. The adiabatic approximation is considered valid in most materials. Here, we show that doped graphene is a spectacular example where this approximation miserably fails.

First-principles calculations of NMR parameters in solids are of crucial importance in chemistry and materials science. The acquisition of a high-resolution spectrum, however, does come with a cost, that is, the suppression of all anisotropies. The interactions that affect NMR spectra are inherently anisotropic and can be represented mathematically by second- and fourth-rank tensors. A third approach is to employ electronic structure techniques that model extended solids using periodic boundary conditions. The linear augmented plane-wave approach (LAPW) through the Wien series of codes has long been used to compute quadrupolar coupling constants. Recoupling experiments are introduced in the context of the measurement of interaction parameters, that is, internuclear distances and anisotropies. The main goal of this section is to highlight the fundamental concepts involved, and the methods required, for experimental measurement parameters. Particular emphasis is placed on important classes of systems such as organic structures and assemblies, inorganic architectures, polymers and hybrids, biomaterials, and nanomaterials.

Innate immunity to viral infection involves induction of the type I IFN response; however, dysfunctional regulation of this pathway leads to inappropriate inflammation. Here, we evaluated a nonconsanguineous family of mixed European descent, with 4 members affected by systemic inflammatory and autoimmune conditions, including lupus, with variable clinical expression. We identified a germline dominant gain-of-function mutation in TMEM173, which encodes stimulator of type I IFN gene (STING), in the affected individuals. STING is a key signaling molecule in cytosolic DNA-sensing pathways, and STING activation normally requires dimerization, which is induced by 2'3' cyclic GMP-AMP (cGAMP) produced by the cGAMP synthase in response to cytosolic DNA. Structural modeling supported constitutive activation of the mutant STING protein based on stabilized dimerization. In agreement with the model predictions, we found that the STING mutant spontaneously localizes in the Golgi of patient fibroblasts and is constitutively active in the absence of exogenous 2'3'-cGAMP in vitro. Accordingly, we observed elevated serum IFN activity and a type I IFN signature in peripheral blood from affected family members. These findings highlight the key role of STING in activating both the innate and adaptive immune responses and implicate aberrant STING activation in features of human lupus.