arXiv subjects

Giulia Galli

Publications and source records attributed to Giulia Galli.

At least 109 records · Page 6Linked to original sources

arXiv2019

All-electron density functional calculations for electron and nuclear spin interactions in molecules and solids

The interaction between electronic and nuclear spins in the presence of external magnetic fields can be described by a spin Hamiltonian, with parameters obtained from first principles, electronic structure calculations. We describe an approach to compute these parameters, applicable to both molecules and solids, which is based on Density Functional Theory (DFT) and real-space, all-electron calculations using finite elements (FE). We report results for hyperfine tensors, zero field splitting tensors (spin-spin component) and nuclear quadrupole tensors of a series of molecules and of the nitrogen-vacancy center in diamond. We compare our results with those of calculations using Gaussian orbitals and plane-wave basis sets, and we discuss their numerical accuracy. We show that calculations based on FE can be systematically converged with respect to the basis set, thus allowing one to establish reference values for the spin Hamiltonian parameters, at a given level of DFT.

cond-mat.mtrl-sci↗

arXiv2019

Computational prediction of lattice thermal conductivity -- a comparison of molecular dynamics and Boltzmann transport approaches

The predictive modeling of lattice thermal conductivity is of fundamental importance for the understanding and design of materials for a wide range of applications. Two major approaches, namely molecular dynamics (MD) simulations and calculations solving approximately the Boltzmann transport equation (BTE), have been developed to compute the lattice thermal conductivity. We present a detailed direct comparison of these two approaches, using as prototypical cases MgO and PbTe. The comparison, carried out using empirical potentials, takes into account the effects of fourth order phonon scattering, temperature-dependent phonon frequencies (phonon renormalization), and investigates the effects of quantum vs. classical statistics. We clarify that equipartition, as opposed to Maxwell Boltzmann, govern the statistics of phonons in MD simulations. We find that lattice thermal conductivity values from MD and BTE show an apparent, satisfactory agreement; however such an agreement is the result of error cancellations. We also show that the primary effect of statistics on thermal conductivity is via the scattering rate dependence on phonon populations.

cond-mat.mtrl-sci↗

arXiv2018

A Finite-field Approach for $GW$ Calculations Beyond the Random Phase Approximation

We describe a finite-field approach to compute density response functions, which allows for efficient $G_0W_0$ and $G_0W_0Γ_0$ calculations beyond the random phase approximation. The method is easily applicable to density functional calculations performed with hybrid functionals. We present results for the electronic properties of molecules and solids and we discuss a general scheme to overcome slow convergence of quasiparticle energies obtained from $G_0W_0Γ_0$ calculations, as a function of the basis set used to represent the dielectric matrix.

physics.chem-ph↗

arXiv2018

Probing spin-phonon interactions in silicon carbide with Gaussian acoustics

Hybrid spin-mechanical systems provide a platform for integrating quantum registers and transducers. Efficient creation and control of such systems require a comprehensive understanding of the individual spin and mechanical components as well as their mutual interactions. Point defects in silicon carbide (SiC) offer long-lived, optically addressable spin registers in a wafer-scale material with low acoustic losses, making them natural candidates for integration with high quality factor mechanical resonators. Here, we show Gaussian focusing of a surface acoustic wave in SiC, characterized by a novel stroboscopic X-ray diffraction imaging technique, which delivers direct, strain amplitude information at nanoscale spatial resolution. Using ab initio calculations, we provide a more complete picture of spin-strain coupling for various defects in SiC with C3v symmetry. This reveals the importance of shear for future device engineering and enhanced spin-mechanical coupling. We demonstrate all-optical detection of acoustic paramagnetic resonance without microwave magnetic fields, relevant to sensing applications. Finally, we show mechanically driven Autler-Townes splittings and magnetically forbidden Rabi oscillations. These results offer a basis for full strain control of three-level spin systems.

quant-ph↗

arXiv2018

Dielectric properties of condensed systems composed of fragments

The dielectric properties of molecules or nanostructures are usually modified in a complex manner, when assembled into a condensed phase. We propose a first-principles method to compute polarizabilities of sub-entities of solids and liquids, which accounts for multipolar interactions at all orders, and is applicable to any semiconductor or insulator. The method only requires the evaluation of induced fields in the condensed phase, with no need of multiple calculations for each constituent. As an example, we present results for the molecular polarizabilities of water in a wide pressure and temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g. to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure this approximation becomes unreliable and in the case of ice X the Clausius-Mossotti relation is not valid.

physics.chem-ph↗

arXiv2017

Electron affinities of water clusters from density-functional and many-body-perturbation theory

In this work, we assess the accuracy of dielectric-dependent hybrid density functionals and many-body perturbation theory methods for the calculation of electron affinities of small water clusters, including hydrogen-bonded water dimer and water hexamer isomers. We show that many-body perturbation theory in the G$_0$W$_0$ approximation starting with the dielectric-dependent hybrid functionals predicts electron affinities of clusters within 0.1 eV of the coupled-cluster results with single, double, and perturbative triple excitations.

physics.chem-ph↗

arXiv2017

Designing defect-based qubit candidates in wide-gap binary semiconductors for solid-state quantum technologies

The development of novel quantum bits is key to extend the scope of solid-state quantum information science and technology. Using first-principles calculations, we propose that large metal ion - vacancy complexes are promising qubit candidates in two binary crystals: 4H-SiC and w-AlN. In particular, we found that the formation of neutral Hf- and Zr-vacancy complexes is energetically favorable in both solids; these defects have spin-triplet ground states, with electronic structures similar to those of the diamond NV center and the SiC di-vacancy. Interestingly, they exhibit different spin-strain coupling characteristics, and the nature of heavy metal ions may allow for easy defect implantation in desired lattice locations and ensure stability against defect diffusion. In order to support future experimental identification of the proposed defects, we report predictions of their optical zero-phonon line, zero-field splitting and hyperfine parameters. The defect design concept identified here may be generalized to other binary semiconductors to facilitate the exploration of new solid-state qubits.

cond-mat.mes-hall↗

arXiv2017

Optimizing surface defects for atomic-scale electronics: Si dangling bonds

Surface defects created and probed with scanning tunneling microscopes are a promising platform for atomic-scale electronics and quantum information technology applications. Using first-principles calculations we demonstrate how to engineer dangling bond (DB) defects on hydrogenated Si(100) surfaces, which give rise to isolated impurity states that can be used in atomic-scale devices. In particular we show that sample thickness and biaxial strain can serve as control parameters to design the electronic properties of DB defects. While in thick Si samples the neutral DB state is resonant with bulk valence bands, ultrathin samples (1-2 nm) lead to an isolated impurity state in the gap; similar behavior is seen for DB pairs and DB wires. Strain further isolates the DB from the valence band, with the response to strain heavily dependent on sample thickness. These findings suggest new methods for tuning the properties of defects on surfaces for electronic and quantum information applications. Finally, we present a consistent and unifying interpretation of many results presented in the literature for DB defects on hydrogenated silicon surfaces, rationalizing apparent discrepancies between different experiments and simulations.

cond-mat.mtrl-sci↗

arXiv2016

Quantum decoherence dynamics of divacancy spins in silicon carbide

Long coherence times are key to the performance of quantum bits (qubits). Here, we experimentally and theoretically show that the Hahn-echo coherence time (T2) of electron spins associated with divacancy defects in 4H-SiC reaches 1.3 ms, one of the longest T2 times of an electron spin in a naturally isotopic crystal. Using a first-principles microscopic quantum-bath model, we find that two factors determine the unusually robust coherence. First, in the presence of moderate magnetic fields (300 G and above), the 29Si and 13C paramagnetic nuclear spin baths are decoupled. In addition, because SiC is a binary crystal, homo-nuclear spin pairs are both diluted and forbidden from forming strongly coupled, nearest-neighbor spin pairs. Longer neighbor distances result in fewer nuclear spin flip-flops, a less fluctuating intra-crystalline magnetic environment, and thus a longer T2 time. Our results point to polyatomic crystals as promising hosts for coherent qubits in the solid state.

cond-mat.mes-hall↗

arXiv2016

The fate of carbon dioxide in water-rich fluids at extreme conditions

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in the Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures (P) and temperatures (T) approximating the conditions of the Earth's upper mantle. Contrary to popular geochemical models assuming that molecular CO$_2$(aq) is the major carbon species present in water under deep earth conditions, we found that at 11 GPa and 1000 K carbon exists almost entirely in the forms of solvated carbonate (CO$_3^{2-}$) and bicarbonate (HCO$_3^-$) ions, and that even carbonic acid (H$_2$CO$_3$(aq)) is more abundant than CO$_2$(aq). Furthermore, our simulations revealed that ion pairing between Na$^+$ and CO$_3^{2-}$/HCO$_3^-$ is greatly affected by P-T conditions, decreasing with increasing pressure at 800$\sim$1000 K. Our results suggest that in the Earth's upper mantle, water-rich geo-fluids transport a majority of carbon in the form of rapidly interconverting CO$_3^{2-}$ and HCO$_3^-$ ions, not solvated CO$_2$(aq) molecules.

physics.chem-ph↗

arXiv2016

Nonempirical Range-separated Hybrid Functionals for Solids and Molecules

Dielectric-dependent hybrid (DDH) functionals were recently shown to yield accurate energy gaps and dielectric constants for a wide variety of solids, at a computational cost considerably less than that of GW calculations. The fraction of exact exchange included in the definition of DDH functionals depends (self-consistently) on the dielectric constant of the material. Here we introduce a range-separated (RS) version of DDH functionals where short and long-range components are matched using system dependent, non-empirical parameters. We show that RS DDHs yield accurate electronic properties of inorganic and organic solids, including energy gaps and absolute ionization potentials. Furthermore we show that these functionals may be generalized to finite systems.

cond-mat.mtrl-sci↗

arXiv2016

Design of defect spins in piezoelectric aluminum nitride for solid-state hybrid quantum technologies

Spin defects in wide-band gap semiconductors are promising systems for the realization of quantum bits, or qubits, in solid-state environments. To date, defect qubits have only been realized in materials with strong covalent bonds. Here, we introduce a strain-driven scheme to rationally design defect spins in functional ionic crystals, which may operate as potential qubits. In particular, using a combination of state-of-the-art ab-initio calculations based on hybrid density functional and many-body perturbation theory, we predicted that the negatively charged nitrogen vacancy center in piezoelectric aluminum nitride exhibits spin-triplet ground states under realistic uni- and bi-axial strain conditions; such states may be harnessed for the realization of qubits. The strain-driven strategy adopted here can be readily extended to a wide range of point defects in other wide-band gap semiconductors, paving the way to controlling the spin properties of defects in ionic systems for potential spintronic technologies.

cond-mat.mtrl-sci↗

arXiv2015

Tetrahedrally coordinated carbonates in Earth's lower mantle

Carbonates are the main species that bring carbon deep into our planet through subduction. They are an important rock-forming mineral group, fundamentally distinct from silicates in Earth's crust in that carbon binds to three oxygen atoms, while silicon is bonded to four oxygens. Here, we present experimental evidence that under the sufficiently high pressures and high temperatures existing in the lower mantle, ferromagnesian carbonates transform to a phase with tetrahedrally coordinated carbons. Above 80 GPa, in situ synchrotron infrared experiments show the unequivocal spectroscopic signature of the high-pressure phase of (Mg,Fe)CO$_3$. Using ab-initio calculations, we assign the new IR signature to C-O bands associated with tetrahedrally coordinated carbon with asymmetric C-O bonds. Tetrahedrally coordinated carbonates are expected to exhibit substantially different reactivity than low pressure three-fold coordinated carbonates, as well as different chemical properties in the liquid state. Hence this may have significant implications on carbon reservoirs and fluxes and the global geodynamic carbon cycle.

cond-mat.mtrl-sci↗

arXiv2015

Large scale GW calculations

We present GW calculations of molecules, ordered and disordered solids and interfaces, which employ an efficient contour deformation technique for frequency integration, and do not require the explicit evaluation of virtual electronic states, nor the inversion of dielectric matrices. We also present a parallel implementation of the algorithm which takes advantage of separable expressions of both the single particle Green's function and the screened Coulomb interaction. The method can be used starting from density functional theory calculations performed with semi-local or hybrid functionals. We applied the newly developed technique to GW calculations of systems of unprecedented size, including water/semiconductor interfaces with thousands of electrons.

cond-mat.mtrl-sci↗

arXiv2015

Self-consistent hybrid functional for condensed systems

A self-consistent scheme for determining the optimal fraction of exact exchange for full-range hybrid functionals is presented and applied to the calculation of band gaps and dielectric constants of solids. The exchange-correlation functional is defined in a similar manner to the PBE0 functional, but the mixing parameter is set equal to the inverse macroscopic dielectric function and it is determined self-consistently by computing the optimal dielectric screening. We found excellent agreement with experiments for the properties of a broad class of systems, with band gaps ranging between 0.7 and 21.7 eV and dielectric constants within 1.23 and 15.9. We propose that the eigenvalues and eigenfunctions obtained with the present self-consistent hybrid scheme may be excellent inputs for G$_0$W$_0$ calculations.

cond-mat.mtrl-sci↗

arXiv2014

The refractive index and electronic gap of water and ice increase with increasing pressure

Determining the electronic and dielectric properties of water at high pressure and temperature is an essential prerequisite to understand the physical and chemical properties of aqueous environments under supercritical conditions, e.g. in the Earth interior. However optical measurements of compressed ice and water remain challenging and it has been common practice to assume that their band gap is inversely correlated to the measured refractive index, consistent with observations reported for hundreds of materials. Here we report ab initio molecular dynamics and electronic structure calculations showing that both the refractive index and the electronic gap of water and ice increase with pressure, at least up to 30 GPa. Subtle electronic effects, related to the nature of interband transitions and band edge localization under pressure, are responsible for this apparently anomalous behavior.

cond-mat.mtrl-sci↗

arXiv2010

Ab initio investigation of the melting line of nitrogen at high pressure

Understanding the behavior of molecular systems under pressure is a fundamental problem in condensed matter physics. In the case of nitrogen, the determination of the phase diagram and in particular of the melting line, are largely open problems. Two independent experiments have reported the presence of a maximum in the nitrogen melting curve, below 90 GPa, however the position and the interpretation of the origin of such maximum differ. By means of ab initio molecular dynamics simulations based on density functional theory and thermodynamic integration techniques, we have determined the phase diagram of nitrogen in the range between 20 and 100 GPa. We find a maximum in the melting line, related to a transformation in the liquid, from molecular N_2 to polymeric nitrogen accompanied by an insulator-to-metal transition.

cond-mat.mtrl-sci↗

arXiv2010

First-Principles Study of Electronic and Vibrational Properties of BaHfN$_2$

The transition metal nitride BaHfN$_2$, which consists of weakly bonded neutral slabs of closed shell ions, has structural and chemical similarities to other layered nitrides which have impressive superconducting T$_c$ when electron doped: A$_x$HfNCl, A$_x$ZrNCl, A$_x$TiNCl, with $T_c= 25.5$, $15.2$ and $16.5$ K, respectively for appropriate donor (A) concentrations $x$. These similarities suggest the possibility of BaHfN$_2$ being another relatively high T$_c$ nitride upon doping, with effects of structure and the role of specific transition metal ions yet to be understood. We report first-principles electronic structure calculations for stoichiometric BaHfN$_2$ using density functional theory with plane-wave basis sets and separable dual-space Gaussian pseudopotentials. An indirect band gap of 0.8 eV was obtained and the lowest conduction band is primarily of Hf 5$d_{xy}$ character, similar to $β$-ZrNCl and $α$-TiNCl. The two N sites, one in the Hf layer and another one in the Ba layer, were found to have very anisotropic Born effective charges (BEC):deviations from the formal charge (-3) are opposite for the two sites, and opposite for the two orientations (in-plane, out of plane). LO-TO splittings and comparison of BECs and dielectric constant tensors to those of related compounds are discussed, and the effect of electron doping on the zone-center phonons is reported.

cond-mat.mtrl-sci↗