arXiv subjects

M. Calandra

Publications and source records attributed to M. Calandra.

At least 19 recordsLinked to original sources

arXiv2022

On the importance of measuring accurately LDOS maps using scanning tunneling spectroscopy in materials presenting atom-dependent charge order: the case of the correlated Pb/Si(111) single atomic layer

We show how to properly extract the local charge order in two-dimensional materials from scanning tunneling microscopy/spectroscopy (STM/STS) measurements. When the charge order presents spatial variations at the atomic scale inside the unit cell and is energy dependent, particular care should be taken. In such cases the use of the lock-in technique, while acquiring an STM topography in closed feedback loop, leads to systematically incorrect dI/dV measurements giving a false local charge order. A correct method is either to perform a constant height measurement or to perform a full grid of dI/dV(V) spectroscopies, using a bias voltage setpoint outside the material bandwidth where the local density-of-states (LDOS) is spatially homogeneous. We take as a paradigmatic example of two-dimensional material the 1/3 single-layer Pb/Si(111). As large areas of this phase cannot be grown, charge ordering in this system is not accessible to angular resolved photoemission or grazing x-ray diffraction. Previous investigations by STM/STS supplemented by {\it ab initio} Density Functional Theory (DFT) calculations concluded that this material undergoes a phase transition to a low-temperature $3\times 3$ reconstruction where one Pb atom moves up, the two remaining Pb atoms shifting down. A third STM/STS study by Adler {\it et al.} [PRL 123, 086401 (2019)] came to the opposite conclusion, i.e. that two Pb atoms move up, while one Pb atom shifts down. This latter erroneous conclusion comes from a misuse of the lock-in technique. In contrast, using a full grid of dI/dV(V) spectroscopy measurements, we show that the energy-dependent LDOS maps agree very well with state-of-the-art DFT calculations confirming the one-up two-down charge ordering. This structural and charge re-ordering in the $3\times 3$ unit cell is equally driven by electron-electron interactions and the coupling to the substrate.

cond-mat.str-el↗

arXiv2018

Chiral spin texture in the charge-density-wave phase of the correlated metallic Pb/Si(111) monolayer

We investigate the 1/3 monolayer $\alpha$-Pb/Si(111) surface by scanning tunneling spectroscopy (STS) and fully relativistic first-principles calculations. We study both the high-temperature $\sqrt{3}\times\sqrt{3}$ and low-temperature $3\times 3$ reconstructions and show that, in both phases, the spin-orbit interaction leads to an energy splitting as large as $25\%$ of the valence-band bandwidth. Relativistic effects, electronic correlations and Pb-substrate interaction cooperate to stabilize a correlated low-temperature paramagnetic phase with well-developed lower and upper Hubbard bands coexisting with $3\times3$ periodicity. By comparing the Fourier transform of STS conductance maps at the Fermi level with calculated quasiparticle interference from non-magnetic impurities, we demonstrate the occurrence of two large hexagonal Fermi sheets with in-plane spin polarizations and opposite helicities.

cond-mat.str-el↗

arXiv2017

Advanced capabilities for materials modelling with Quantum ESPRESSO

Quantum ESPRESSO 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 pseudo-potential and projector-augmented-wave approaches. Quantum ESPRESSO 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 theirs 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.

cond-mat.mtrl-sci↗

arXiv2017

X-ray Magnetic and Natural Circular Dichroism from first principles: Calculation of K- and L1-edge spectra

An efficient first principles approach to calculate X-ray magnetic circular dichroism (XMCD) and X-ray natural circular dichroism (XNCD) is developed and applied in the near edge region at the K-and L1-edges in solids. Computation of circular dichroism requires precise calculations of X-ray absorption spectra (XAS) for circularly polarized light. For the derivation of the XAS cross section, we used a relativistic description of the photon-electron interaction that results in an additional term in the cross-section that couples the electric dipole operator with an operator $\mathbf{\sigma}\cdot (\mathbf{\epsilon} \times \mathbf{r})$ that we name spin-position. The numerical method relies on pseudopotentials, on the gauge including projected augmented wave method and on a collinear spin relativistic description of the electronic structure. We apply the method to the calculations of K-edge XMCD spectra of ferromagnetic iron, cobalt and nickel and of I L1-edge XNCD spectra of $\alpha$-LiIO3, a compound with broken inversion symmetry. For XMCD spectra we find that, even if the electric dipole term is the dominant one, the electric quadrupole term is not negligible (8% in amplitude in the case of iron). The term coupling the electric dipole operator with the spin-position operator is significant (28% in amplitude in the case of iron). We obtain a sum-rule relating this new term to the spin magnetic moment of the p-states. In $\alpha$-LiIO3 we recover the expected angular dependence of the XNCD spectra.

cond-mat.other↗

arXiv2015

Wannier interpolation of the electron-phonon matrix elements in polar semiconductors: Polar-optical coupling in GaAs

We generalize the Wannier interpolation of the electron-phonon matrix elements to the case of polar-optical coupling in polar semiconductors. We verify our methodological developments against experiments, by calculating the widths of the electronic bands due to electron-phonon scattering in GaAs, the prototype polar semiconductor. The calculated widths are then used to estimate the broadenings of excitons at critical points in GaAs and the electron-phonon relaxation times of hot electrons. Our findings are in good agreement with available experimental data. Finally, we demonstrate that while the Fr\"ohlich interaction is the dominant scattering process for electrons/holes close to the valley minima, in agreement with low-field transport results, at higher energies, the intervalley scattering dominates the relaxation dynamics of hot electrons or holes. The capability of interpolating the polar-optical coupling opens new perspectives in the calculation of optical absorption and transport properties in semiconductors and thermoelectrics.

cond-mat.mtrl-sci↗

arXiv2014

Electron localization and possible phase separation in the absence of a charge density wave in single-phase 1T-VS$_2$

We report on a systematic study of the structural, magnetic and transport properties of high-purity 1T-VS$_2$ powder samples prepared under high pressure. The results differ notably from those previously obtained by de-intercalating Li from LiVS$_2$. First, no Charge Density Wave (CDW) is found by transmission electron microscopy down to 94 K. Though, \textit{ab initio} phonon calculations unveil a latent CDW instability driven by an acoustic phonon softening at the wave vector ${\bf q}_{CDW} \approx$ (0.21,0.21,0) previously reported in de-intercalated samples. A further indication of latent lattice instability is given by an anomalous expansion of the V-S bond distance at low temperature. Second, infrared optical absorption and electrical resistivity measurements give evidence of non metallic properties, consistent with the observation of no CDW phase. On the other hand, magnetic susceptibility and NMR data suggest the coexistence of localized moments with metallic carriers, in agreement with \textit{ab initio} band structure calculations. This discrepancy is reconciled by a picture of electron localization induced by disorder or electronic correlations leading to a phase separation of metallic and non-metallic domains in the nm scale. We conclude that 1T-VS$_2$ is at the verge of a CDW transition and suggest that residual electronic doping in Li de-intercalated samples stabilizes a uniform CDW phase with metallic properties.

cond-mat.mtrl-sci↗

arXiv2012

K-edge X-ray absorption spectra in transition metal oxides beyond the single particle approximation: shake-up many body effects

The near edge structure (XANES) in K-edge X-ray absorption spectroscopy (XAS) is a widely used tool for studying electronic and local structure in materials. The precise interpretation of these spectra with the help of calculations is hence of prime importance, especially for the study of correlated materials which have a complicated electronic structure per se. The single particle approach, for example, has generally limited itself to the dominant dipolar cross-section. It has long been known however that effects beyond this approach should be taken into account, both due to the inadequacy of such calculations when compared to experiment and the presence of shake-up many-body satellites in core-level photoemission spectra of correlated materials. This effect should manifest itself in XANES spectra and the question is firstly how to account for it theoretically and secondly how to verify it experimentally. By using state-of-the-art first principles electronic structure calculations and 1s photoemission measurements we demonstrate that shake-up many-body effects are present in K-edge XAS dipolar spectra of NiO, CoO and CuO at all energy scales. We show that shake-up effects can be included in K-edge XAS spectra in a simple way by convoluting the single-particle first-principles calculations including core-hole effects with the 1s photoemission spectra. We thus describe all features appearing in the XAS dipolar cross-section of NiO and CoO and obtain a dramatic improvement with respect to the single-particle calculation in CuO. These materials being prototype correlated magnetic oxides, our work points to the presence of shake-up effects in K-edge XANES of most correlated transition metal compounds and shows how to account for them, paving the way to a precise understanding of their electronic structure.

cond-mat.mtrl-sci↗

arXiv2011

Hole-depletion of ladders in Sr$_{14}$Cu$_{24}$O$_{41}$ induced by correlation effects

The hole distribution in Sr$_{14}$Cu$_{24}$O$_{41}$ is studied by low temperature polarization dependent O K Near-Edge X-ray Absorption Fine Structure measurements and state of the art electronic structure calculations that include core-hole and correlation effects in a mean-field approach. Contrary to all previous analysis, based on semi-empirical models, we show that correlations and antiferromagnetic ordering favor the strong chain hole-attraction. For the remaining small number of holes accommodated on ladders, leg-sites are preferred to rung-sites. The small hole affinity of rung-sites explains naturally the 1D - 2D cross-over in the phase diagram of (La,Y,Sr,Ca)$_{14}$Cu$_{24}$O$_{41}$

cond-mat.str-el↗

arXiv2011

Comparative study of the phonons in non-superconducting BaC6 and superconducting CaC6 using inelastic x-ray scattering

The low energy phonons of two different graphite intercalation compounds (GICs) have been measured as a function of temperature using inelastic x-ray scattering (IXS). In the case of the non-superconductor BaC6, the phonons observed are significantly higher (up to 20 %) in energy than those predicted by theory, in contrast to the reasonable agreement found in superconducting CaC6. Additional IXS intensity is observed below 15 meV in both BaC6 and CaC6. It has been previously suggested that this additional inelastic intensity may arise from defect or vacancy modes in these compounds, unpredicted by theory (d'Astuto et al, Phys. Rev. B 81 104519 (2010)). Here it is shown that this additional intensity can arise directly from the large disorder of the available samples. Our results show that future theoretical work is required to understand the relationship between the crystal structure, the phonons and the superconductivity in GICs.

cond-mat.supr-con↗

arXiv2009

Neutron scattering study of the high energy graphitic phonons in superconducting CaC$_6$

We present the results of a neutron scattering study of the high energy phonons in the superconducting graphite intercalation compound CaC$_6$. The study was designed to address hitherto unexplored aspects of the lattice dynamics in CaC$_6$, and in particular any renormalization of the out-of-plane and in-plane graphitic phonon modes. We present a detailed comparison between the data and the results of density functional theory (DFT). A description is given of the analysis methods developed to account for the highly-textured nature of the samples. The DFT calculations are shown to provide a good description of the general features of the experimental data. This is significant in light of a number of striking disagreements in the literature between other experiments and DFT on CaC$_6$. The results presented here demonstrate that the disagreements are not due to any large inaccuracies in the calculated phonon frequencies.

cond-mat.supr-con↗

arXiv2009

Multiple pre-edge structures in Cu K-edge of high Tc cuprates revealed by high resolution x-ray absorption spectroscopy

Using high resolution x-ray absorption spectroscopy and state-of-the-art electronic structure calculations we demonstrate that the pre-edge region at the Cu K-edge of high T$_c$ cuprates is composed of several excitationsinvisible in standard X-ray absorption spectra. We consider in detail the case of Ca$_{2-x}$CuO$_2$Cl$_2$ and show that the many pre-edge excitations (two for c-axis polarization, four for in-plane polarization and out-of-plane incident X-ray momentum) are dominated by off-site transitions and intersite hybridization. This demonstrates the relevance of approaches beyond the single-site model for the description of the pre-edges of correlated materials. Finally, we show the occurrence of a doubling of the main edge peak that is most visible when the polarization is along the c-axis. This doubling, that has not been seen in any previous absorption data in cuprates, is not reproduced by first principles calculations. We suggest that this peak is due to many-body charge-transfer excitations, while all the other visible far-edge structures are single particle in origin. Our work indicates that previous interpretations of the Cu K-edge X-ray absorption spectra in high T$_c$ cuprates can be profitably reconsidered.

cond-mat.mtrl-sci↗

arXiv2009

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.

cond-mat.mtrl-sci↗

arXiv2008

Measuring the intrinsic charge transfer gap using K-edge X-ray absorption spectroscopy

Pre-edge features in X-ray absorption spectroscopy contain key information about the lowest excited states and thus on the most interesting physical properties of the system. In transition metal oxides they are particularly structured but extracting physical parameters by comparison with a calculation is not easy due to several computational challenges. By combining core-hole attraction and correlation effects in first principles approach, we calculate Ni K-edge X-ray absorption spectra in NiO. We obtain a striking, parameter-free agreement with experimental data and show that dipolar pre-edge features above the correlation gap are due to non-local excitations largely unaffected by the core-hole. We show that in charge transfer insulators, this property can be used to measure the correlation gap and probe the intrinsic position of the upper-Hubbard band.

cond-mat.mtrl-sci↗

arXiv2008

Pressure-induced order-disorder phase transition in superconducting CaC6

By means of synchrotron X-ray diffraction, we studied the effect of high pressure, P, up to 13 GPa on the room temperature crystal structure of superconducting CaC6. In this P range, no change of the pristine space group symmetry, \textit{R\=3m}, is found. However, at 9 GPa, i.e. close to the critical value at which a large T_c reduction was reported recently, we observed a compressibility jump concomitant to a large broadening of Bragg peaks. The reversibility of both effects upon depressurization and symmetry arguments give evidence of an order-disorder phase transition of second order, presumably associated with the Ca sublattice, which provides a full account for the above Tc reduction.

cond-mat.supr-con↗

arXiv2006

Electronic thermal conductivity at high temperatures: Violation of the Wiedemann-Franz law in narrow band metals

We study the electronic part of the thermal conductivity kappa of metals. We present two methods for calculating kappa, a quantum Monte-Carlo (QMC) method and a method where the phonons but not the electrons are treated semiclassically (SC). We compare the two methods for a model of alkali-doped C60, A3C60, and show that they agree well. We then mainly use the SC method, which is simpler and easier to interpret. We perform SC calculations for Nb for large temperatures T and find that kappa increases with T as kappa(T)=a+bT, where a and b are constants, consistent with a saturation of the mean free path, l, and in good agreement with experiment. In contrast, we find that for A3C60, kappa(T) decreases with T for very large T. We discuss the reason for this qualitatively in the limit of large T. We give a quantum-mechanical explanation of the saturation of l for Nb and derive the Wiedemann-Franz law in the limit of T much smaller than W, where W is the band width. In contrast, due to the small W of A3C60, the assumption T much smaller than W can be violated. We show that this leads to kappa(T) \sim T^{-3/2} for very large T and a strong violation of the Wiedemann-Franz law.

cond-mat.mtrl-sci↗

arXiv2006

Evidence for non-conventional pairing in Na$\_x$CoO$\_2$$\cdot$yH$\_2$O

We report on first investigation of the lattice dynamics in the novel superconducting material Na$\_{0.35}$CoO$\_2$$\cdot$1.3H$\_2$O and the non-hydrated parent compound Na$\_{0.7}$CoO$\_2$ by inelastic x-ray scattering. The measured phonon dispersion along the $Γ-M$ direction show a marked softening with hole doping of two optical phonon branches close to the Brillouin zone boundary. The phonon spectra, dispersion, and softening are well reproduced by first-principle calculations. The calculations indicates that the soft branches are mainly composed of Co-vibration modes. The estimation of the critical temperature based on electron-phonon coupling mechanism undisputedly points to a non-conventional superconducting state in this material.

cond-mat.str-el↗

arXiv2005

Polarized resonant inelastic x-ray scattering as an ultra-fine probe of excited states in La2CuO4

X-ray absorption is the standard method to probe the unoccupied density of states at a given edge. Here we show that polarized Resonant Inelastic X-Ray Scattering in La2CuO4 at the Cu K-edge is extremely sensitive to the environment of the Cu atom and the fine structure in the Cu 4p density of states. Combined ab initio and many-body cluster calculations, used for the first time in such a context, show remarkable agreement with experiment. In particular we identify a non-local effect namely a transition to off-site Cu 3d states.

cond-mat.str-el↗

arXiv2003

Dynamical properties of a strongly correlated model for quarter-filled layered organic molecular crystals

The dynamical properties of an extended Hubbard model, which is relevant to quarter-filled layered organic molecular crystals, are analyzed. We have computed the dynamical charge correlation function, spectral density, and optical conductivity using Lanczos diagonalization and large-N techniques. As the ratio of the nearest-neighbour Coulomb repulsion, V, to the hopping integral, t, increases there is a transition from a metallic phase to a charge ordered phase. Dynamical properties close to the ordering transition are found to differ from the ones expected in a conventional metal. Large-N calculations display an enhancement of spectral weight at low frequencies as the system is driven closer to the charge ordering transition in agreement with Lanczos calculations. As V is increased the charge correlation function displays a plasmon-like mode which, for wavevectors close to (pi,pi), increases in amplitude and softens as the charge ordering transition is approached. We propose that inelastic X-ray scattering be used to detect this mode. Large-N calculations predict superconductivity with dxy symmetry close to the ordering transition. We find that this is consistent with Lanczos diagonalization calculations, on lattices of 20 sites, which find that the binding energy of two holes becomes negative close to the charge ordering transition.

cond-mat.str-el↗