Stefano Fabris

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). 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.

Dual Path Mechanism in the Thermal Reduction of Graphene Oxide

Graphene is easily produced by thermally reducing graphene oxide. However, defect formation in the C network during deoxygenation compromises the charge carrier mobility in the reduced material. Understanding the mechanisms of the thermal reactions is essential for defining alternative routes able to limit the density of defects generated by carbon evolution. Here, we identify a dual path mechanism in the thermal reduction of graphene oxide driven by the oxygen coverage: at low surface density, the O atoms adsorbed as epoxy groups evolve as O(2) leaving the C network unmodified. At higher coverage, the formation of other O-containing species opens competing reaction channels, which consume the C backbone. We combined spectroscopic tools and ab initio calculations to probe the species residing on the surface and those released in the gas phase during heating and to identify reaction pathways and rate-limiting steps. Our results illuminate the current puzzling scenario of the low temperature gasification of graphene oxide.

A stabilization mechanism of zirconia based on oxygen vacancies only

Abstract The microscopic mechanism leading to stabilization of cubic and tetragonal forms of zirconia (ZrO2) is analyzed by means of a self-consistent tight-binding model. Using this model, energies and structures of zirconia containing different vacancy concentrations are calculated, equivalent in concentration to the charge compensating vacancies associated with dissolved yttria (Y2O3) in the tetragonal and cubic phase fields (3.2 and 14.4% mol, respectively). The model is shown to predict the large relaxations around an oxygen vacancy, and the clustering of vacancies along the 111 directions, in good agreement with experiments and first principles calculations. The vacancies alone are shown to explain the stabilization of cubic zirconia, and the mechanism is analyzed.

Reaction Mechanisms for the CO Oxidation on Au/CeO2 Catalysts: Activity of Substitutional Au3+/Au+ Cations and Deactivation of Supported Au+ Adatoms

Density functional theory calculations that account for the on-site Coulomb interaction via a Hubbard term (DFT+U) reveal the mechanisms for the oxidation of CO catalyzed by isolated Au atoms as well as small clusters in Au/CeO(2) catalysts. Ceria (111) surfaces containing positively charged Au ions, either as supported Au(+) adatoms or as substitutional Au(3+) ions, are shown to activate molecular CO and to catalyze its oxidation to CO(2). In the case of supported single Au(+) adatoms, the limiting rate for the CO oxidation is determined by the adsorbate spillover from the adatom to the oxide support. The reaction then proceeds with the CO oxidation via lattice oxygen and O vacancy formation. These vacancies are shown to readily attract the supported Au(+) adatoms and to turn them into negatively charged Au(delta-) adspecies that deactivate the catalyst, preventing further CO adsorption. Au(3+) ions dispersed into the ceria lattice as substitutional point defects can instead sustain a full catalytic cycle consisting of three individual steps maintaining their activity along the reaction process: Au cations in Au(x)Ce(1-x)O(2) systems promote multiple oxidations of CO without any activation energy via formation of surface O vacancies. Molecular oxygen adsorbs at these vacancies and forms O adspecies that then catalyze the oxidation of molecular CO, closing the catalytic cycle and recovering the stoichiometric Au(x)Ce(1-x)O(2) system. The interplay between the reversible Ce(4+)/Ce(3+) and Au(3+)/Au(+) reductions underpins the high catalytic activity of dispersed Au atoms into the ceria substrate. It is shown that the positive oxidation state of the substitutional Au ions is retained along the catalytic cycle, thus preventing the deactivation of Au(x)Ce(1-x)O(2) catalysts in operation conditions. Finally, although a single Au(+) adatom bound to an O vacancy is shown to deactivate during CO oxidation, the calculations predict that the reactivity of gold nanoparticles nucleated at O vacancies can be recovered for cluster sizes as small as Au(2).

Nanofaceted PdO Sites in PdCe Surface Superstructures: Enhanced Activity in Catalytic Combustion of Methane†

An open superstructure: A Pd/CeO2 catalyst prepared by solution combustion synthesis is three to five times more active for CH4 combustion than the best conventional palladium-based systems. The catalyst contains an ordered, stable Pd-O-Ce surface superstructure (see picture; cyan arrow is a square-planar Pd site, red arrow is an undercoordinated O atom) and is an example of ultra-highly dispersed, stable PdO within an oxide carrier.

Electronic structure of surface-supported bis(phthalocyaninato) terbium(III) single molecular magnets.

The electronic structure of isolated bis(phthalocyaninato) terbium(III) molecules, a novel single-molecular-magnet (SMM), supported on the Cu(111) surface has been characterized by density functional theory and scanning tunneling spectroscopy. These studies reveal that the interaction with the metal surface preserves both the molecular structure and the large spin magnetic moment of the metal center. The 4f electron states are not perturbed by the adsorption while a strong molecular/metal interaction can induce the suppression of the minor spin contribution delocalized over the molecular ligands. The calculations show that the inherent spin magnetic moment of the molecule is only weakly affected by the interaction with the surface and suggest that the SMM character might be preserved.

Mechanisms for oxidative unzipping and cutting of graphene.

We identify mechanisms and surface precursors for the nucleation and growth of extended defects on oxidized graphene. Density functional theory calculations show that the formation of surface structures capable to initiate the unzipping and cracking of the oxidized C network is strongly influenced by the constraint of the graphitic lattice on the surface functional groups. Accounting for this effect on the preferential spatial patterning of O adsorbates allows us to revise and extend the current models of graphene oxidative unzipping and cutting. We find that these processes are rate limited by O diffusion and driven by the local strain induced by the O adspecies. Adsorbate mobility is ultimately recognized as a key factor to control and to prevent the C-network breakdown during thermal processing of oxidized graphene.

Creating single-atom Pt-ceria catalysts by surface step decoration

Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces—monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt2+ ions in planar PtO4 moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt2+ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts.

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals. This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free-energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behavior above the transition temperature.