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Alfredo Pasquarello

Publications and source records attributed to Alfredo Pasquarello.

At least 19 recordsLinked to original sources
PubMed2006

Mixed Wannier-Bloch functions for electrons and phonons in periodic systems.

We introduce mixed Wannier-Bloch functions for studying electronic and vibrational spectra of periodic systems. These functions carry both spatial localization and limited spectral broadening, thereby combining the advantages of descriptions based on energy eigenstates (Bloch states) and position eigenstates (Wannier states). For the analysis of vibrational modes, a lattice position operator is introduced, analogous to the electronic Berry-phase position operator. Application to vitreous SiO2 demonstrates that mixed Wannier-Bloch functions constitute a powerful tool for tracking fingerprints of short- and medium-range structural order in electronic and vibrational spectra.

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PubMed2006

Origin of fine structure in si photoelectron spectra at silicon surfaces and interfaces.

Using a first-principles approach, we investigate the origin of the fine structure in Si 2p photoelectron spectra at the Si(100)-(2 x 1) surface and at the Si(100)-SiO2 interface. Calculated and measured shifts show very good agreement for both systems. By using maximally localized Wannier functions, we clearly identify the shifts resulting from the electronegativity of second-neighbor atoms. The other shifts are then found to be proportional to the average bond-length variation around the Si atom. Hence, in combination with accurate modeling, photoelectron spectroscopy can provide a direct measure of the strain field at the atomic scale.

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PubMed2005

Infrared spectra at surfaces and interfaces from first principles: evolution of the spectra across the Si(100)-SiO2 interface.

We introduce a general scheme for calculating from first principles both the transverse-optical and longitudinal-optical infrared absorption spectra at surfaces or interfaces. A spatial decomposition of the spectra gives the evolution of the infrared activity across the considered system. Application to ultrathin oxides on silicon yields infrared spectra which reproduce the observed redshift of the high-frequency peaks for decreasing oxide thicknesses. This effect is shown to arise from the lengthening of the Si-O bonds in the substoichiometric oxide at the interface.

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PubMed2005

An electronegativity-induced spin repulsion effect.

We present a spin delocalization effect in radical Si-containing systems, featuring a heteroatom of high electronegativity (such as N, O, or Cl) bonded to the unsaturated Si atom. We find that the higher the electronegativity of the heteroatom, the more the localized spin shifts away from the unsaturated Si atom and the heteroatom toward saturated Si neighbors. We demonstrate that this spin repulsion toward saturated Si atoms is induced by the electronegativity difference between the Si atom and the heteroatoms. We present a simple molecular-orbital-based mechanism which fully explains the structural and electronic effects. We contrast the present spin delocalization mechanism with the classical hyperconjugation in organic chemistry. The most important consequences of this spin redistribution are the electron-spin-resonance activity of the saturated Si neighbors and the enhanced stability of the radical centers. We predict a similar effect for Ge radicals and discuss why organic systems based on carbon do not feature such spin repulsion.

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PubMed2005

Fraction of boroxol rings in vitreous boron oxide from a first-principles analysis of Raman and NMR spectra.

We determine the fraction f of B atoms belonging to boroxol rings in vitreous boron oxide through a first-principles analysis. After generating a model structure of vitreous B2O3 by first-principles molecular dynamics, we address a large set of properties, including the neutron structure factor, the neutron density of vibrational states, the infrared spectra, the Raman spectra, and the 11B NMR spectra, and find overall good agreement with corresponding experimental data. From the analysis of Raman and 11B NMR spectra, we yield consistently for both probes a fraction f of approximately 0.75. This result indicates that the structure of vitreous boron oxide is largely dominated by boroxol rings.

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PubMed2005

Medium-range structural properties of vitreous germania obtained through first-principles analysis of vibrational spectra.

We analyze the principal vibrational spectra of vitreous GeO(2) and derive therefrom structural properties referring to length scales beyond the basic tetrahedral unit. We generate a model structure that yields a neutron structure factor in accord with experiment. The inelastic-neutron, the infrared, and the Raman spectra, calculated within a density-functional approach, also agree with respective experimental spectra. The accord for the Raman spectrum supports a Ge-O-Ge angle distribution centered at 135 degrees. The Raman feature X(2) is found to result from vibrations in three-membered rings, and therefore constitutes a distinctive characteristic of the medium-range structure.

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PubMed2005

Ab initio molecular dynamics of liquid hydrogen chloride.

We carried out an ab initio molecular dynamics simulation of liquid hydrogen chloride (l-HCl) at a temperature of 313 K. Comparison with inelastic neutron scattering data shows that the simulation achieves an overall good description of the structural correlations, improving significantly upon a description based on classical interaction potentials. Despite some minor differences between theory and experiment in the H-H partial structure factor, the simulation gives a description of the hydrogen bonding in impressive agreement with experiment, for both the amount and the bond-length distribution of the bonds. In the simulation, 40% of the molecules are nonbonded, while the hydrogen-bonded chains are short, principally consisting of dimers (25%) and trimers (15%). Neighboring molecules in the simulation are found to form L-shaped arrangements, like in the isolated (HCl)(2) dimer and in crystalline phases of HCl. The time correlation of the molecular-axis orientation is found to be characterized by a very short decay time (0.13 ps), consistent with the short length of the hydrogen-bonded chains. Other dynamical properties investigated in this work include the diffusion coefficient and the vibrational density of states. We evaluated the molecular dipole of the HCl molecule in the liquid using a definition based on the coupling of rotational modes to an external electric field. The average dipole moment (1.53 D) derived in this way is found to be considerably larger than for the isolated molecule (1.11 D). Our results show that the dipole moment in [script-l]-HCl undergoes large fluctuations, both in orientation and in modulus. Upon the onset of an external field, such dipole fluctuations concur to reduce the fluctuations of the dielectric response.

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PubMed2004

Modeling phase separation in nonstoichiometric silica.

We have modeled the decomposition of nonstoichiometric amorphous SiOx upon annealing into silicon and stoichiometric silica, using a new method based on mapping Metropolis Monte Carlo simulations onto rate equations. The concentrations of all oxidation states of silicon are derived as a function of time and found to attain steady-state values at long times dependent on temperature T and oxygen content x. The degree of phase separation and the sizes of Si particles are predicted as a function of T and x, enabling greater control over the size of silicon quantum dots in silica matrices.

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PubMed2004

Reaction of the oxygen molecule at the Si(100)-SiO2 interface during silicon oxidation.

Using constrained ab initio molecular dynamics, we investigate the reaction of the O2 molecule at the Si(100)-SiO2 interface during Si oxidation. The reaction proceeds sequentially through the incorporation of the O2 molecule in a Si-Si bond and the dissociation of the resulting network O2 species. The oxidation reaction occurs nearly spontaneously and is exothermic, irrespective of the O2 spin state or of the amount of excess negative charge available at the interface. The reaction evolves through the generation of network coordination defects associated with charge transfers. Our investigation suggests that the Si oxidation process is fully governed by diffusion.

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PubMed2003

Dielectric discontinuity at interfaces in the atomic-scale limit: permittivity of ultrathin oxide films on silicon.

Using a density-functional approach, we study the dielectric permittivity across interfaces at the atomic scale. Focusing on the static and high-frequency permittivities of SiO2 films on silicon, for oxide thicknesses from 12 A down to the atomic scale, we find a departure from bulk values in accord with experiment. A classical three-layer model accounts for the calculated permittivities and is supported by the microscopic polarization profile across the interface. The local screening varies on length scales corresponding to first-neighbor distances, indicating that the dielectric transition is governed by the chemical grading. Silicon-induced gap states are shown to play a minor role.

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PubMed2003

Supported fe nanoclusters: evolution of magnetic properties with cluster size.

Using a density functional approach, we study structural and magnetic properties of small Fe(n) clusters (n<or=8) deposited on a MgO(100) substrate. Upon deposition, the clusters closely preserve their gas-phase structure. The magnetic moments for the adsorbed clusters exceed the value for bulk Fe. Compared to the gas phase, significant reductions in the magnetic moments are found for Fe(n) clusters with n<or=6. These reductions result from intracluster charge rearrangements caused by interaction with O 2p orbitals, rather than from structural deformations or charge transfer from the surface. As the cluster size increases, the gas-phase magnetic moments are recovered.

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PubMed2003

Transition structure at the Si(100)-SiO2 interface.

We characterize the transition structure at the Si(100)-SiO2 interface by addressing the inverse ion-scattering problem. We achieve sensitivity to Si displacements at the interface by carrying out ion-scattering measurements in the channeling geometry for varying ion energies. To interpret our experimental results, we generate realistic atomic-scale models using a first-principles approach and carry out ion-scattering simulations based on classical interatomic potentials. Silicon displacements larger than 0.09 A are found to propagate for three layers into the Si substrate, ruling out a transition structure with regularly ordered O bridges, as recently proposed.

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PubMed2003

Concentration of small ring structures in vitreous silica from a first-principles analysis of the Raman spectrum.

Using a first-principles approach, we calculate Raman spectra for a model structure of vitreous silica. We develop a perturbational method for calculating the dielectric tensor in an ultrasoft pseudopotential scheme and obtain Raman coupling tensors by finite differences with respect to atomic displacements. For frequencies below 1000 cm(-1), the parallel-polarized Raman spectrum of vitreous silica is dominated by oxygen bending motions, showing a strong sensitivity to the intermediate range structure. By modeling the Raman coupling, we derive estimates for the concentrations of three- and four-membered rings from the experimental intensities of the Raman defect lines.

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PubMed2002

Pressure-induced structural changes in liquid SiO2 from Ab initio simulations.

First-principles molecular dynamics simulations at constant pressure have been used to investigate the mechanisms of compression of liquid SiO2. Liquid SiO2 is found to become denser than quartz at a pressure of about 6 GPa, in agreement with extrapolations of lower pressure experimental data. The high compressibility of the liquid is traced to medium-range changes in the topology of the atomic network. These changes consist in an increase of network connectivity caused by the pressure-induced appearance of coordination defects.

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PubMed2002

Ab initio molecular dynamics investigation of the structure and the noncollinear magnetism in liquid oxygen: occurrence of O4 molecular units.

We modeled liquid oxygen using ab initio molecular dynamics in which both the atomic structure and the noncollinear magnetic structure evolve without constraints. The atomic structure shows preference for parallel alignment of first-neighbor molecules and is supported by an excellent agreement between theoretical and experimental nuclear structure factors. The magnetic structure shows short-range antiferromagnetic correlations in agreement with spin-polarized neutron diffraction data. The observed correlations primarily result from appropriate trajectories of colliding O2 molecules. The simulation provides evidence for the occurrence of long-living O4 molecular units.

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PubMed2002

Ab initio molecular dynamics in a finite homogeneous electric field.

We treat homogeneous electric fields within density functional calculations with periodic boundary conditions. A nonlocal energy functional depending on the applied field is used within an ab initio molecular dynamics scheme. The reliability of the method is demonstrated in the case of bulk MgO for the Born effective charges, and the high- and low-frequency dielectric constants. We evaluate the static dielectric constant by performing a damped molecular dynamics in an electric field and avoiding the calculation of the dynamical matrix. Application of this method to vitreous silica shows good agreement with experiment and illustrates its potential for systems of large size.

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PubMed2002

Dielectric constants of Zr silicates: a first-principles study.

Using density-functional theory, we compute the optical and static dielectric constants for a set of Zr silicates modeled by various SiO2 crystals, with Zr atoms substitutional to Si, and by an amorphous structure. We then derive a microscopic scheme that relates the dielectric constants to structural units centered on Si and Zr atoms through the definition of characteristic parameters. Applied to amorphous (ZrO2)(x)(SiO2)(1-x), these schemes describe the observed dependence of the dielectric constants on the Zr concentration and highlight the role of ZrO6 units.

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