First-principles characterization of Mg low-index surfaces: Structure, reconstructions, and surface core-level shifts

In this paper, first-principles calculations provide structural characterization of three low-index Mg surfaces - Mg(0001), Mg(1010), and Mg(1120) - and their respective surface core-level shifts (SCLSs). Inspired by the close similarities between Be and Mg surfaces, we also explore the reconstruction of Mg(1120). Through the calculation of surface energies and the use of the angular-component decomposed density of states, we show that reconstructions are likely to occur at the Mg(1120) surface, similarly to what was found earlier for Be(1120). Indeed, the surface energy of some of the explored reconstructions is slightly lower than that of the unreconstructed surface. In addition, because of lattice symmetry, the morphology of the unreconstructed surface (1120) results in a steplike zig-zag chain packing, with topmost chains supporting a resonant, quasi-one-dimensional (1D), partially filled electronic state. As the presence of partially filled quasi-1D bands is a necessary condition for Peierls-like dimerization, we verify that the undimerized surface chain remains stable with respect to it. Some of the reconstructions, namely, the 2 71 and 3 71 added row reconstructions, induce a stronger relaxation of the topmost chains, increasing the coupling with lower layers and thus significantly damping the quasi-1D character of this state. The original approach followed offers a common and general framework to identify quasi-1D bands - even in the case of resonant electronic surface states - and to meaningfully compare calculated and measured SCLSs even in the presence of multicomponent peak contributions

Collective dipole effects in ionic transport under electric fields

In the context of ionic transport in solids, the variation of a migration barrier height under electric fields is traditionally assumed to be equal to the classical electric work of a point charge that carries the transport charge. However, how reliable is this phenomenological model and how does it fare with respect to Modern Theory of Polarization? In this work, we show that such a classical picture does not hold in general as collective dipole effects may be critical. Such effects are unraveled by an appropriate polarization decomposition and by an expression that we derive, which defines the equivalent polarization-work charge. The equivalent polarization-work charge is not equal neither to the transported charge, nor to the Born effective charge of the migrating atom alone, but it is defined by the total polarization change at the transition state. Our findings are illustrated by oxygen charged defects in MgO and in SiO2

v-P 2 O 5 micro-clustering in P-doped silica studied by a first-principles Raman investigation

Synthetic vitreous silica is currently the preferred material for the production of optical fibres because of the several excellent properties of this glass, e.g. high transmission in the visible and IR domains, high mechanical strength, chemical durability, and ease of doping with various materials. For instance, fiber lasers and amplifiers exploit the light amplification properties provided by rare-earth ions employed as dopants in the core of silica-based optical fibers. The structure and composition of the nearest neighbor shell surrounding rare-earth ions in silica-based optical fibers and amplifiers have been intensively debated in the last decade. To reduce aggregation effects between rare-earth ions, co-dopants such as phosphorus and aluminium are added as structural modifiers; phosphorus-doping, in particular, has proved to be very efficient in dissolving rare-earth ions. In this work, we provide further insights concerning the embedding of P atoms into the silica network, which may be relevant for explaining the ease of formation of a phosphorus pentoxide nearest-neighbor shell around a rare-earth dopant. In particular, by means of first-principles calculations, we discuss alternative models for an irradiation (UV, x\u2013, \u3b3-rays) induced paramagnetic center, i.e. the so called room-temperature phosphorus-oxygen-hole center, and its precursors. We report that the most likely precursor of a room-temperature phosphorus-oxygen-hole center comprises of a micro-cluster of a few (at least two) neighboring phosphate tetrahedra, and correspondingly that the occurrence of isolated [(O-) 2 P(=O) 2 ] 12 units is unlikely even at low P-doping concentrations. In fact, this work predicts that the symmetric stretching of P=O bonds in isolated [(O-) 2 P(=O) 2 ] 12 units appears as a Raman band at a frequency of ~1110 cm 121 , and only by including at least another corner-sharing phosphate tetrahedron, it is shown to shift to higher frequencies (up to ~40 cm 121 ) due to the shortening of P=O bonds, thereby leading to an improved agreement with the observed Raman band located at ~1145 cm 121

O2 Loaded Germanosilicate Optical Fibers: Experimental In Situ Investigation and Ab Initio Simulation Study of GLPC Evolution under Irradiation

In this work we present a combined experimental and ab initio simulation investigation concerning the Germanium Lone Pair Center (GLPC), its interaction with molecular oxygen (O2), and evolution under irradiation. First, O2 loading has been applied here to Ge-doped optical fibers to reduce the concentration of GLPC point defects. Next, by means of cathodoluminescence in situ experiments, we found evidence that the 10 keV electron irradiation of the treated optical fibers induces the generation of GLPC centers, while in nonloaded optical fibers, the irradiation causes the bleaching of the pre-existing GLPC. Ab initio calculations were performed to investigate the reaction of the GLPC with molecular oxygen. Such investigations suggested the stability of the dioxagermirane (DIOG) bulk defect, and its back conversion into GLPC with a local release of O2 under irradiation. Furthermore, it is also inferred that a remarkable portion of the O2 passivated GLPC may form Ge tetrahedra connected to peroxy bridges. Such structures may have a larger resistance to the irradiation and not be back converted into GLPC

Vibrational and structural properties of P2O5P_2O_5 glass: Advances from a combined modeling approach

We present experimental measurements and ab initio simulations of the crystalline and amorphous phases of $P_2O_5$. The calculated Raman, infrared, and vibrational density of states (VDOS) spectra are in excellent agreement with experimental measurements and contain the signatures of all the peculiar local structures of the amorphous phase, namely, bridging and nonbridging (double-bonded or terminal) oxygens and tetrahedral $PO_4$ units associated with $Q^2$, $Q^3$, and $Q^4$ species ($Q^n$ denotes the various types of $PO_4$ tetrahedra, with $n$ being the number of bridging oxygen atoms that connect the tetrahedra to the rest of the network). In order to reveal the internal structure of the vibrational spectrum, the characteristics of vibrational modes in different frequency ranges are investigated using a mode-projection approach at different symmetries based on the $T_d$ symmetry group. In particular, the VDOS spectrum in the range from $∼ 600$ to $870$ $cm^-$$^1$ is dominated by bending ($F_2$$_b$) motions related to bridging oxygen and phosphorus ($∼ 800$ $cm^-$$^1$ band) atoms, while the high-frequency doublet zone ($∼ 870 – 1250$ $cm^-$$^1$ is associated mostly with the asymmetric (($F_2$$_s$) and symmetric ($A_1$) stretching modes, and most prominent peak around $1400$ $cm^-$$^1$ (exp. $1380$ $cm^-$$^1$) is mainly due to asymmetric stretching vibrations supported by double-bonded oxygen atoms. The lower-frequency range below $600$ $cm^-$$^1$ is shown to arise from a mixture of bending ($E$ and ($F_2$$_b$) and rotation ($F_1$) modes. The scissors bending ($E$) and rotation ($F_1$) modes are well localized below $600$ $cm^-$$^1$, whereas the ($F_2$$_b$ bending modes spread further into the range $∼ 600 – 870$ $cm^-$$^1$. The projections of the eigenmodes onto $Q^2$, $Q^3$, and $Q^4$ species yield well-defined contributions at frequencies in striking correspondence with the positions of the Raman and infrared bands

Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials

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.Comment: 36 pages, 5 figures, resubmitted to J.Phys.: Condens. Matte

SaX: An open source package for electronic-structure and optical-properties calculations in the GW approximation

We present here SaX (Self-energies and eXcitations), a plane-waves package aimed at electronic-structure and optical-properties calculations in the GW framework, namely using the GW approximation for quasiparticle properties and the Bethe-Salpeter equation for the excitonic effects. The code is mostly written in FORTRAN90 in a modern style, with extensive use of data abstraction (i.e. objects). Sax employs state of the art techniques and can treat large systems. The package is released with an open source license and can be also download from http://www.sax-project.org/

SaX: An open source package for electronic-structure and optical-properties calculations in the GW approximation

This program has been imported from the CPC Program Library held at Queen's University Belfast (1969-2018) Abstract We present here SaX (Self-energies and eXcitations), a plane-waves package aimed at electronic-structure and optical-properties calculations in the GW framework, namely using the GW approximation for quasi-particle properties and the Bethe–Salpeter equation for the excitonic effects. The code is mostly written in FORTRAN90 in a modern style, with extensive use of data abstraction (i.e. objects). SaX employs state of the art techniques and can treat large systems. The package is released with ... Title of program: SaX (Self-energies and eXcitations) Catalogue Id: AEDF_v1_0 Nature of problem SaX is designed to calculate the electronic band-structure of semiconductors, including quasi-particle effects and optical properties including excitonic effects. Versions of this program held in the CPC repository in Mendeley Data AEDF_v1_0; SaX (Self-energies and eXcitations); 10.1016/j.cpc.2009.02.00

Supporting information: Optical properties of saturated and unsaturated carbonyl defects in polyethylene

International audiencePolyethylene (PE), one of the simplest and most used aliphatic polymers, is generally provided with a number of additives, in particular antioxidants, because of its tendency to get oxidized. Carbonyl defects, a product of the oxidation of PE, are occurring in various forms, in particular saturated ones, known as ketones, where a C=O double bond substitutes a CH$_2$ group, andvarious unsaturated ones, i.e., with further missing hydrogens. Many experimental investigations of the optical properties in the visible-UV range mainly attribute thephotoluminescence of PE to one specific kind of unsaturated carbonyls, following analogies to the emission spectra of similar small molecules. However, the reason why saturated carbonyls should not be optically detected is not clear. We investigated the optical properties of PE with and without carbonyl defects using perturbative GW and the Bethe-Salpeter equation in order to take intoaccount excitonic effects. We discuss the calculated excitonic states in comparison with experimental absorption-emission energies and the stability of both saturated and unsaturated carbonyl defects. We conclude that the unsaturated defects are indeed the best candidate for the luminescence ofoxidized PE, and the reason is mainly due to oscillator strengths