arXiv subjects

Francesco Mauri

Publications and source records attributed to Francesco Mauri.

At least 37 records · Page 2Linked to original sources

arXiv2025

Electron-phonon interaction and phonons in 2d doped semiconductors

Electron-phonon interaction and phonon frequencies of doped polar semiconductors are sensitive to long-range Coulomb forces and can be strongly affected by screening effects of free carriers, the latter changing significantly when approaching the two-dimensional limit. We tackle this problem within a linear-response dielectric-matrix formalism, where screening effects can be properly taken into account by generalized effective charge functions and the inverse scalar dielectric function, allowing for controlled approximations in relevant limits. We propose complementary computational methods to evaluate from first principles both effective charges -- encompassing all multipolar components beyond dynamical dipoles and quadrupoles -- and the static dielectric function of doped two-dimensional semiconductors, and provide analytical expressions for the long-range part of the dynamical matrix and the electron-phonon interaction in the long-wavelength limit. As a representative example, we apply our approach to study the impact of doping in disproportionated graphene, showing that optical Fröhlich and acoustic piezoelectric couplings, as well as the slope of optical longitudinal modes, are strongly reduced, with a potential impact on the electronic/intrinsic scattering rates and related transport properties.

cond-mat.mtrl-sci↗

arXiv2025

Ab-initio Van der Waals electrodynamics: polaritons and electron scattering from plasmons and phonons in BN-capped graphene

Plasmons and polar phonons are elementary electrodynamic excitations of matter. In 2d and at long wavelengths, they couple to light and act as the system polaritons. They also dictate the scattering of charged carriers. Van der Waals heterostructures offer the opportunity to couple excitations from different layers via long-range Coulomb interactions, modifying both their dispersion and their scattering of electrons. Even when the excitations do not couple, they are still influenced by the screening from all layers, leading to complex dynamical interactions between electrons, plasmons and polar phonons. We develop an efficient ab initio model to solve the dynamical electric response of Van der Waals heterostructures, accompanied by a formalism to extract relevant spectroscopic and transport quantities. Notably, we obtain scattering rates for electrons of the heterostructure coupling remotely with electrodynamic excitations. We apply those developments to BN-capped graphene, in which polar phonons from BN couple to plasmons in graphene. We study the nature of the coupled excitations, their dispersion and their coupling to graphene's electrons. Regimes driven by either phonons or plasmons are identified, as well as a truly hybrid regime at long wavelengths. Those are studied as a function of the graphene's Fermi level and the number of BN layers. In contrast with descriptions in terms of surface-optical phonons, we find that the electron-phonon interaction stems from different modes. Moreover, the dynamical screening of the coupling between BN's LO phonons and graphene's electrons crosses over from inefficient to metal-like depending on the relative value of the phonons' frequency and the energetic onset of interband transitions. While the coupling is significant in general, the associated scattering of graphene's carriers is found to be negligible in the context of electronic transport.

cond-mat.mtrl-sci↗

arXiv2025

Variational formulation of dynamical electronic response functions in presence of nonlocal exchange interactions

We consider the dynamical electronic response function in theoretical frameworks that include nonlocal exchange interactions, such as the Bethe-Salpeter equation with the frequency independent approximation of the screened interaction, Hartree-Fock, and range-separated Hybrid DFT approaches. Within these pictures, we demonstrate that any time-dependent electronic linear response function allows for a formulation which is variational in the electronic density matrix. To achieve our goal, we consider the usual form of a response function, written in terms of a screened and a bare electronic vertices (`bare-screen'), and perform an exact rewriting in terms of purely screened electronic vertices (`screen-screen'). Within the `screen-screen' formulation, the response function can be written as a stationary point of a functional of the exact density matrix. Further, we show that the imaginary part of any electronic response can be written in the form of a generalized Fermi Golden Rule, by introducing an exact complementary rewriting in terms of vertices related by complex conjugation (`screen*-screen'). The screen-screen formulation can be further extended partitioning the electronic interaction in separate contributions, expressing the response in terms of partially screened electronic vertices (`partial screen-partial screen'), preserving the stationary properties. We numerically validate the effectiveness of our formalism by calculating the optical conductivity of graphene, which exhibits strong excitonic effects. To do so, we solve the Bethe-Salpeter Equation on a tight-binding model, including exchange effects in the response of graphene. Our findings show the advantages of the variationality of the screen-screen formulation over the others both in convergence properties and robustness with density-matrix approximations.

cond-mat.mtrl-sci↗

arXiv2025

Electron-phonon interaction and longitudinal-transverse phonon splitting in doped semiconductors

We study the effect of doping on the electron-phonon interaction and on the phonon frequencies in doped semiconductors, taking into account the screening in presence of free carriers at finite temperature. We study the impact of screening on the Fröhlich-like vertex and on the long-range components of the dynamical matrix, going beyond the state-of-the-art description for undoped crystals, thanks to the development of a computational method based on maximally localized Wannier functions. We apply our approach to cubic silicon carbide, where in presence of doping the Fröhlich coupling and the longitudinal-transverse phonon splitting are strongly reduced, thereby influencing observable properties such as the electronic lifetime.

cond-mat.mtrl-sci↗

arXiv2025

Probing enhanced electron-phonon coupling in graphene by infrared resonance Raman spectroscopy

We report on resonance Raman spectroscopy measurements with excitation photon energy down to 1.16 eV on graphene, to study how low-energy carriers interact with lattice vibrations. Thanks to the excitation energy close to the Dirac point at $\mathbf{K}$, we unveil a giant increase of the intensity ratio between the double-resonant 2D and 2D$^\prime$ peaks with respect to that measured in graphite. Comparing with fully \textit{ab initio} theoretical calculations, we conclude that the observation is explained by an enhanced, momentum-dependent coupling between electrons and Brillouin zone-boundary optical phonons. This finding applies to two dimensional Dirac systems and has important consequences for the modeling of transport in graphene devices operating at room temperature.

cond-mat.mes-hall↗

arXiv2025

Giant piezoelectricity driven by Thouless pump in conjugated polymers

Piezoelectricity of organic polymers has attracted increasing interest because of several advantages they exhibit over traditional inorganic ceramics. While most organic piezoelectrics rely on the presence of intrinsic local dipoles, a highly nonlocal electronic polarization can be foreseen in conjugated polymers, characterised by delocalized and highly responsive $π$-electrons. These 1D systems represent a physical realization of a Thouless pump, a mechanism of adiabatic charge transport of topological nature which results, as shown in this work, in anomalously large dynamical effective charges, inversely proportional to the band gap energy. A structural (ferroelectric) phase transition further contributes to an enhancement of the piezoelectric response reminiscent of that observed in piezoelectric perovskites close to morphotropic phase boundaries. First-principles Density Functional Theory (DFT) calculations performed in two representative conjugated polymers using hybrid functionals, show that state-of-the-art organic piezoelectric are outperformed by piezoelectric conjugated polymers, mostly thanks to strongly anomalous effective charges of carbon, larger than 5e - ordinary values being of the order of 1e - and reaching the giant value of 30e for band gaps of the order of 1 eV.

cond-mat.mtrl-sci↗

arXiv2025

Born effective charges and vibrational spectra in super and bad conducting metals

Interactions mediated by electron-phonon coupling are responsible for important cooperative phenomena in metals such as superconductivity and charge-density waves. The same interaction mechanisms produce strong collision rates in the normal phase of correlated metals, causing sizeable reductions of the dc conductivity and reflectivity. As a consequence, low-energy excitations like phonons, which are crucial for materials characterization, become visible in optical infrared spectra. A quantitative assessment of vibrational resonances requires the evaluation of dynamical Born effective charges, which quantify the coupling between macroscopic electric fields and lattice deformations. We show that the Born effective charges of metals crucially depend on the collision regime of conducting electrons. In particular, we describe, within a first principles framework, the impact of electron scattering on the infrared vibrational resonances, from the undamped, collisionless regime to the overdamped, collision-dominated limit. Our approach enables the interpretation of vibrational reflectance measurements of both super and bad conducting metals, as we illustrate for the case of strongly electron-phonon coupled superhydride H$_3$S.

cond-mat.mtrl-sci↗

arXiv2024

Beyond Gaussian fluctuations of quantum anharmonic nuclei. The case of rotational degrees of freedom

The atomic motion in molecular crystals, such as high-pressure hydrogen or hybrid organic-inorganic perovskites, is very complex due to quantum anharmonic effects. In addition, these materials accommodate rotational degrees of freedom. All the approximate methods that describe the nuclei thermodynamics using Cartesian coordinates lead to an unphysical hybridization of roto-librations with other high-energy modes. Hence, they do not accurately account for the free energy contributions of these degrees of freedom. So, a reliable description of a molecular crystal's phase diagram is only possible with Path Integral Molecular Dynamics (PIMD) at a high computational cost. This work shows how to include roto-librational modes in the Self-Consistent Harmonic Approximation (SCHA) framework. SCHA approximates the nuclei Cartesian fluctuations to be Gaussian, thus neglecting curvilinear motion. Keeping its low computational cost, we employ the generalization of SCHA, called nonlinear SCHA (NLSCHA). Our method relies on a Gaussian \textit{ansatz} for the nuclei density matrix on a curved manifold, allowing us to map roto-librations into harmonic modes defined on a surface. By optimizing the surface's curvature variationally, we minimize the free energy, allowing the spontaneous activation of these degrees of freedom without external parameters. Notably, in the limit of vanishing curvature, we recover the standard SCHA.

cond-mat.mtrl-sci↗

arXiv2024

Beyond Gaussian fluctuations of quantum anharmonic nuclei

The Self-Consistent Harmonic Approximation (SCHA) describes atoms in solids, including quantum fluctuations and anharmonic effects, in a non-perturbative way. It computes ionic free energy variationally, constraining the atomic quantum-thermal fluctuations to be Gaussian. Consequently, the entropy is analytical; there is no need for thermodynamic integration or heavy diagonalization to include finite temperature effects. In addition, as the probability distribution is fixed, SCHA solves all the equations with Monte Carlo integration without employing Metropolis sampling of the quantum phase space. Unfortunately, the Gaussian approximation breaks down for rotational modes and tunneling effects. We show how to describe these non-Gaussian fluctuations using the quantum variational principle at finite temperatures, keeping the main advantage of SCHA: direct access to free energy. Our method, nonlinear SCHA (NLSCHA), employs an invertible nonlinear transformation to map Cartesian coordinates into an auxiliary manifold parametrized by a finite set of variables. So, we adopt a Gaussian \textit{ansatz} for the density matrix in this new coordinate system. The nonlinearity of the mapping ensures that NLSCHA enlarges the SCHA variational subspace, and its invertibility conserves the information encoded in the density matrix. We evaluate the entropy in the auxiliary space, where it has a simple analytical form. As in the SCHA, the variational principle allows for optimizing free parameters to minimize free energy. Finally, we show that, for the first time, NLSCHA gives direct access to the entropy of a crystal with non-Gaussian degrees of freedom.

cond-mat.mtrl-sci↗

arXiv2024

Temperature-invariant heat conductivity from compensating crystalline and glassy transport: from the Steinbach meteorite to furnace bricks

The thermal conductivities of crystals and glasses vary strongly and with opposite trends upon heating, decreasing in crystals and increasing in glasses. Here, we show--both with first-principles predictions based on the Wigner transport equation and with thermoreflectance experiments--that the dominant transport mechanisms of crystals (particle-like propagation) and glasses (wave-like tunnelling) can coexist and compensate in materials with crystalline bond order and nearly glassy bond geometry. We demonstrate that ideal compensation emerges in a sample of silica in the form of tridymite, carved from a meteorite found in Steinbach (Germany) in 1724, and yields a "propagation-tunneling-invariant" (PTI) conductivity that is independent from temperature and intermediate between the opposite trends of $α$-quartz crystal and silica glass. We show how such PTI conductivity occurs in the quantum regime below the Debye temperature, and can largely persist at high temperatures in a geometrically amorphous tridymite phase found in refractory bricks fired for years in furnaces for steel smelting. Last, we discuss implications to heat transfer in solids exposed to extreme temperature variations, ranging from planetary cooling to heating protocols to reduce the carbon footprint of industrial furnaces.

cond-mat.mtrl-sci↗

arXiv2024

Large impact of phonon lineshapes on the superconductivity of solid hydrogen

Phonon anharmonicity plays a crucial role in determining the stability and vibrational properties of high-pressure hydrides. Furthermore, strong anharmonicity can render phonon quasiparticle picture obsolete questioning standard approaches for modeling superconductivity in these material systems. In this work, we show the effects of non-Lorentzian phonon lineshapes on the superconductivity of high-pressure solid hydrogen. We calculate the superconducting critical temperature T$_\mathrm{C}$ \emph{ab initio} considering the full phonon spectral function and show that it overall enhances the T$_\mathrm{C}$ estimate. The anharmonicity-induced phonon softening exhibited in spectral functions increases the estimate of the critical temperature, while the broadening of phonon lines due to phonon-phonon interaction decreases it. Our calculations also reveal that superconductivity emerges in hydrogen in the $Cmca-12$ molecular phase VI at pressures between 450 and 500 GPa and explain the disagreement between the previous theoretical results and experiments.

cond-mat.supr-con↗

arXiv2024

Quantum effects in the H-bond symmetrization and in the thermodynamic properties of high pressure ice

We investigate the structural and thermodynamic properties of high-pressure ice by incorporating quantum anharmonicity at a non-perturbative level. Quantum fluctuations reduce the critical pressure of the phase transition between phase VIII (with asymmetric H-bonds) and phase X (with symmetric H-bonds) by 65 GPa from its classical value of 116 GPa at 0K. Moreover, quantum effects make it temperature-independent over a wide temperature range (0K-300K), in agreement with experimental estimates obtained through vibrational spectroscopy and in striking contrast to the strong temperature dependence found in the classical approximation. The equation of state shows fingerprints of the transition in accordance with experimental evidence. Additionally, we demonstrate that, within our approach, proton disorder in phase VII has a negligible impact on the occurrence of phase X. Finally, we reproduce with high accuracy the 10 GPa isotope shift due to the hydrogen-to-deuterium substitution.

cond-mat.other↗

arXiv2024

Infrared resonance Raman of bilayer graphene: signatures of massive fermions and band structure on the 2D peak

Few-layer graphene possesses low-energy carriers which behave as massive fermions, exhibiting intriguing properties in both transport and light scattering experiments. Lowering the excitation energy of resonance Raman spectroscopy down to 1.17 eV we target these massive quasiparticles in the split bands close to the K point. The low excitation energy weakens some of the Raman processes which are resonant in the visible, and induces a clearer frequency-separation of the sub-structures of the resonance 2D peak in bi- and trilayer samples. We follow the excitation-energy dependence of the intensity of each sub-structure and, comparing experimental measurements on bilayer graphene with ab initio theoretical calculations, we trace back such modifications on the joint effects of probing the electronic dispersion close to the band splitting and enhancement of electron-phonon matrix elements.

cond-mat.mes-hall↗

arXiv2024

Theory of infrared double-resonance Raman spectrum in graphene: the role of the zone-boundary electron-phonon enhancement

We theoretically investigate the double-resonance Raman spectrum of monolayer graphene down to infrared laser excitation energies. By using first-principles density functional theory calculations, we improve upon previous theoretical predictions based on conical models or tight-binding approximations, and rigorously justify the evaluation of the electron-phonon enhancement found in Ref. [Venanzi, T., Graziotto, L. et al., Phys. Rev. Lett. 130, 256901 (2023)]. We proceed to discuss the effects of such enhancement on the room temperature graphene resistivity, hinting towards a possible reconciliation of theoretical and experimental discrepancies.

cond-mat.mes-hall↗

arXiv2023

Electronic structure and lattice dynamics of 1T-VSe$_2$: origin of the 3D-CDW

In order to characterize in detail the charge density wave (CDW) transition of 1$T$-VSe$_2$, its electronic structure and lattice dynamics are comprehensively studied by means of x-ray diffraction, angle resolved photoemission (ARPES), diffuse and inelastic x-ray scattering (IXS), and state-of-the-art first principles density functional theory calculations. Resonant elastic x-ray scattering (REXS) does not show any resonant enhancement at either V or Se K-edges, indicating that the CDW peak describes a purely structural modulation of the electronic ordering. ARPES identifies (i) a pseudogap at T$>$T$_{CDW}$, which leads to a depletion of the density of states in the $ML-M'L'$ plane at T$<$T$_{CDW}$, and (ii) anomalies in the electronic dispersion reflecting a sizable impact of phonons on it. A diffuse scattering precursor, characteristic of soft phonons, is observed at room temperature (RT) and leads to the full collapse of the low-energy phonon ($ω_1$) with propagation vector (0.25 0 -0.3) r.l.u. We show that the frequency and linewidth of this mode are anisotropic in momentum space, reflecting the momentum dependence of the electron-phonon interaction (EPI), hence demonstrating that the origin of the CDW is, to a much larger extent, due to the momentum dependence EPI with a small contribution from nesting. The pressure dependence of the $ω_1$ soft mode remains nearly constant up to 13 GPa at RT, with only a modest softening before the transition to the high-pressure monoclinic $C2/m$ phase. The wide set of experimental data are well captured by our state-of-the art first-principles anharmonic calculations with the inclusion of van der Waals (vdW) corrections in the exchange-correlation functional. The description of the electronics and dynamics of VSe$_2$ reported here adds important pieces of information to the understanding of the electronic modulations of TMDs.

cond-mat.str-el↗

arXiv2023

EPIq : an open-source software for the calculation of electron-phonon interaction related properties

EPIq (Electron-Phonon wannier Interpolation over k and q-points) is an open-source software for the calculation of electron-phonon interaction related properties from first principles.Acting as a post-processing tool for a density-functional perturbation theory code ( Quantum ESPRESSO ) and wannier90, EPIq exploits the localization of the deformation potential in the Wannier function basis and the stationary properties of a force-constant functional with respect to the first-order perturbation of the electronic charge density to calculate many electron-phonon related properties with high accuracy and free from convergence issues related to Brillouin zone sampling. EPIq features includes: the adiabatic and non-adiabatic phonon dispersion, superconducting properties (including the superconducting band gap in the Migdal-Eliashberg formulation), double-resonant Raman spectra and lifetime of excited carriers. The possibility to customize most of its input makes EPIq a versatile and interoperable tool. Particularly relevant is the interaction with the Stochastic Self-Consistent Harmonic Approximation (SSCHA) allowing anharmonic effects to be included in the calculation of electron-properties. The scalability offered by the Wannier representation combined with a straightforward workflow and easy-to-read input and output files make EPIq accessible to the wide condensed matter and material science communities.

cond-mat.mtrl-sci↗

arXiv2023

Bending rigidity, sound propagation and ripples in flat graphene

Despite many of the applications of graphene rely on its uneven stiffness and high thermal conductivity, the mechanical properties of graphene, and in general of all 2D materials, are still elusive. The harmonic theory predicts a quadratic dispersion for the flexural acoustic vibrational mode, which leads the unphysical result that long wavelength in-plane acoustic modes decay before vibrating one period, preventing the propagation of sound. The robustness of the quadratic dispersion has been questioned by arguing that the anharmonic phonon-phonon interaction linearizes it. However, this implies a divergent bending rigidity in the long wavelength limit not reproduced experimentally. Here we show that rotational symmetry protects the quadratic flexural dispersion against phonon-phonon interactions and that, consequently, the bending stiffness is non-divergent irrespective of the temperature. Our non-perturbative anharmonic calculations also determine that sound propagation coexists with a quadratic dispersion. We also show that the temperature dependence of the height fluctuations of the membrane, known as ripples, is fully determined by thermal or quantum fluctuations, but without the anharmonic suppression of their amplitude previously assumed. The universality of our conclusions reconcile experimental evidence and theory not just in graphene, but all 2D materials.

cond-mat.mes-hall↗

arXiv2023

Wigner Gaussian dynamics: simulating the anharmonic and quantum ionic motion

The atomic motion controls important features of materials, such as thermal transport, phase transitions, and vibrational spectra. However, the simulation of ionic dynamics is exceptionally challenging when quantum fluctuations are relevant (e.g., at low temperatures or with light atoms) and the energy landscape is anharmonic. In this work, we formulate the Time-Dependent Self-Consistent Harmonic Approximation (TDSCHA) in the Wigner framework, paving the way for the efficient computation of the nuclear motion in systems with sizable quantum and thermal anharmonic fluctuations. Besides the improved numerical efficiency, the Wigner formalism unveils the classical limit of TDSCHA and provides a link with the many-body perturbation theory of Feynman diagrams. We further extend the method to account for the non-linear couplings between phonons and photons, responsible, e.g., for a nonvanishing Raman signal in high-symmetry Raman inactive crystals, firstly discussed by Rasetti and Fermi. We benchmark the method in phase III of high-pressure hydrogen ab initio. The nonlinear photon-phonon coupling reshapes the IR spectra and explains the high-frequency shoulder of the H2 vibron observed in experiments. The Wigner TDSCHA is computationally cheap and derived from first principles: it is unbiased by assumptions on the phonon-phonon and phonon-photon scattering and does not depend on empirical parameters. Therefore, the method can be adopted in unsupervised high-throughput calculations.

cond-mat.mtrl-sci↗