arXiv subjects

Federico Grasselli

Publications and source records attributed to Federico Grasselli.

At least 37 records · Page 2Linked to original sources

arXiv2024

Thermal transport of glasses via machine learning driven simulations

Accessing the thermal transport properties of glasses is a major issue for the design of production strategies of glass industry, as well as for the plethora of applications and devices where glasses are employed. From the computational standpoint, the chemical and morphological complexity of glasses calls for atomistic simulations where the interatomic potentials are able to capture the variety of local environments, composition, and (dis)order that typically characterize glassy phases. Machine-learning potentials (MLPs) are emerging as a valid alternative to computationally expensive ab initio simulations, inevitably run on very small samples which cannot account for disorder at different scales, as well as to empirical force fields, fast but often reliable only in a narrow portion of the thermodynamic and composition phase diagrams. In this article, we make the point on the use of MLPs to compute the thermal conductivity of glasses, through a review of recent theoretical and computational tools and a series of numerical applications on vitreous silica and vitreous silicon, both pure and intercalated with lithium.

cond-mat.dis-nn↗

arXiv2024

Mechanism of charge transport in lithium thiophosphate

Lithium ortho-thiophosphate (Li$_3$PS$_4$) has emerged as a promising candidate for solid-state-electrolyte batteries, thanks to its highly conductive phases, cheap components, and large electrochemical stability range. Nonetheless, the microscopic mechanisms of Li-ion transport in Li$_3$PS$_4$ are far to be fully understood, the role of PS$_4$ dynamics in charge transport still being controversial. In this work, we build machine learning potentials targeting state-of-the-art DFT references (PBEsol, r$^2$SCAN, and PBE0) to tackle this problem in all known phases of Li$_3$PS$_4$ ($α$, $β$ and $γ$), for large system sizes and timescales. We discuss the physical origin of the observed superionic behavior of Li$_3$PS$_4$: the activation of PS$_4$ flipping drives a structural transition to a highly conductive phase, characterized by an increase of Li-site availability and by a drastic reduction in the activation energy of Li-ion diffusion. We also rule out any paddle-wheel effects of PS$_4$ tetrahedra in the superionic phases -- previously claimed to enhance Li-ion diffusion -- due to the orders-of-magnitude difference between the rate of PS$_4$ flips and Li-ion hops at all temperatures below melting. We finally elucidate the role of inter-ionic dynamical correlations in charge transport, by highlighting the failure of the Nernst-Einstein approximation to estimate the electrical conductivity. Our results show a strong dependence on the target DFT reference, with PBE0 yielding the best quantitative agreement with experimental measurements not only for the electronic band-gap but also for the electrical conductivity of $β$- and $α$-Li$_3$PS$_4$.

cond-mat.mtrl-sci↗

arXiv2023

Experimental anonymous quantum conferencing

Anonymous quantum conference key agreement (AQCKA) allows a group of users within a network to establish a shared cryptographic key without revealing their participation. Although this can be achieved using bi-partite primitives alone, it is costly in the number of network rounds required. By allowing the use of multi-partite entanglement, there is a substantial efficiency improvement. We experimentally implement the AQCKA task in a six-user quantum network using Greenberger-Horne-Zeilinger (GHZ)-state entanglement and obtain a significant resource cost reduction in line with theory when compared to a bi-partite-only approach. We also demonstrate that the protocol retains an advantage in a four-user scenario with finite key effects taken into account.

quant-ph↗

arXiv2023

Self-interaction and transport of solvated electrons in molten salts

The dynamics of (few) electrons dissolved in an ionic fluid--as when a small amount of metal is added to a solution while upholding its electronic insulation--manifests interesting properties that can be ascribed to nontrivial topological features of particle transport (e.g., Thouless' pumps). In the adiabatic regime, the charge distribution and the dynamics of these dissolved electrons are uniquely determined by the nuclear configuration. Yet, their localization into effective potential wells and their diffusivity are dictated by how the self-interaction is modeled. In this article, we investigate the role of self-interaction in the description of localization and transport properties of dissolved electrons in non-stoichiometric molten salts. Although the account for the exact (Fock) exchange strongly localizes the dissolved electrons, decreasing their tunneling probability and diffusivity, we show that the dynamics of the ions and of the dissolved electrons are largely uncorrelated, irrespective of the degree to which the electron self-interaction is treated, and in accordance with topological arguments.

physics.chem-ph↗

arXiv2023

Conference key agreement in a quantum network

Quantum conference key agreement (QCKA) allows multiple users to establish a secure key from a shared multi-partite entangled state. In a quantum network, this protocol can be efficiently implemented using a single copy of a N-qubit Greenberger-Horne-Zeilinger (GHZ) state to distil a secure N-user conference key bit, whereas up to N-1 entanglement pairs are consumed in the traditional pair-wise protocol. We demonstrate the advantage provided by GHZ states in a testbed consisting of a photonic six-user quantum network, where four users can distil either a GHZ state or the required number of Bell pairs for QCKA using network routing techniques. In the asymptotic limit, we report a more than two-fold enhancement of the conference key rate when comparing the two protocols. We extrapolate our data set to show that the resource advantage for the GHZ protocol persists when taking into account finite-key effects.

quant-ph↗

arXiv2023

Satellite-Based Quantum Key Distribution in the Presence of Bypass Channels

The security of prepare-and-measure satellite-based quantum key distribution (QKD), under restricted eavesdropping scenarios, is addressed. We particularly consider cases where the eavesdropper, Eve, has limited access to the transmitted signal by Alice, and/or Bob's receiver station. This restriction is modeled by lossy channels between Alice/Bob and Eve, where the transmissivity of such channels can, in principle, be bounded by monitoring techniques. An artefact of such lossy channels is the possibility of having {\it bypass} channels, those which are not accessible to Eve, but may not necessarily be characterized by the users either. This creates interesting, unexplored, scenarios for analyzing QKD security. In this paper, we obtain generic bounds on the key rate in the presence of bypass channels and apply them to continuous-variable QKD protocols with Gaussian encoding with direct and reverse reconciliation. We find regimes of operation in which the above restrictions on Eve can considerably improve system performance. We also develop customised bounds for several protocols in the BB84 family and show that, in certain regimes, even the simple protocol of BB84 with weak coherent pulses is able to offer positive key rates at high channel losses, which would otherwise be impossible under an unrestricted Eve. In this case the limitation on Eve would allow Alice to send signals with larger intensities than the optimal value under an ideal Eve, which effectively reduces the effective channel loss. In all these cases, the part of the transmitted signal that does not reach Eve can play a non-trivial role in specifying the achievable key rate. Our work opens up new security frameworks for spaceborne quantum communications systems.

quant-ph↗

arXiv2023

Robustness of Local Predictions in Atomistic Machine Learning Models

Machine learning (ML) models for molecules and materials commonly rely on a decomposition of the global target quantity into local, atom-centered contributions. This approach is convenient from a computational perspective, enabling large-scale ML-driven simulations with a linear-scaling cost, and also allow for the identification and post-hoc interpretation of contributions from individual chemical environments and motifs to complicated macroscopic properties. However, even though there exist practical justifications for these decompositions, only the global quantity is rigorously defined, and thus it is unclear to what extent the atomistic terms predicted by the model can be trusted. Here, we introduce a quantitative metric, which we call the local prediction rigidity (LPR), that allows one to assess how robust the locally decomposed predictions of ML models are. We investigate the dependence of LPR on the aspects of model training, particularly the composition of training dataset, for a range of different problems from simple toy models to real chemical systems. We present strategies to systematically enhance the LPR, which can be used to improve the robustness, interpretability, and transferability of atomistic ML models.

physics.chem-ph↗

arXiv2023

Effect of a Temperature Gradient on the Screening Properties of Ionic Fluids

The electrostatic screening properties of ionic fluids are of paramount importance in countless physical processes. Yet, the behavior of ionic conductors out of thermal equilibrium has to date mainly been studied in the context of thermodiffusion phenomena by virtue of direct extensions of Debye-Hückel theories. We investigate how the static response of a symmetric ionic fluid is influenced by the presence of a thermal gradient by introducing a theory of electrostatic screening under a stationary temperature profile. By borrowing mathematical methods commonly used in the semiclassical approximation of quantum particles, we find analytical solutions to the asymptotic decay of the charge density which can be used to describe the non-equilibrium response of the system to external charge perturbations and for arbitrary ionic concentrations. Notably, a transition between monotonic and oscillatory screening regimes is observed as an effect of the temperature variation which generalizes known results of thermal equilibrium to out of equilibrium conditions. A final quantitative example on the screening of charged surfaces in aqueous electrolytes shows that the deviation from thermal equilibrium predicted by our solutions is generally larger than thermodiffusion effects, and should therefore be taken into account for a comprehensive description of the electrical double layer. Our findings pave the way to the rigorous treatment of non-equilibrium steady states in ionic systems with potential applications to the study of energy materials, nanostructured systems and waste-heat-recovery technologies.

cond-mat.stat-mech↗

arXiv2023

Boosting device-independent cryptography with tripartite nonlocality

Device-independent (DI) protocols, such as DI conference key agreement (DICKA) and DI randomness expansion (DIRE), certify private randomness by observing nonlocal correlations when two or more parties test a Bell inequality. While most DI protocols are restricted to bipartite Bell tests, harnessing multipartite nonlocal correlations may lead to better performance. Here, we consider tripartite DICKA and DIRE protocols based on testing multipartite Bell inequalities, specifically: the Mermin-Ardehali-Belinskii-Klyshko (MABK) inequality, and the Holz and the Parity-CHSH inequalities introduced in the context of DICKA protocols. We evaluate the asymptotic performance of the DICKA (DIRE) protocols in terms of their conference key rate (net randomness generation rate), by deriving lower bounds on the conditional von Neumann entropy of one party's outcome and two parties' outcomes. For the Holz inequality, we prove a tight analytical lower bound on the one-outcome entropy and conjecture a tight lower bound on the two-outcome entropy. We additionally re-derive the analytical one-outcome entropy bound for the MABK inequality with a much simpler method and obtain a numerical lower bound on the two-outcome entropy for the Parity-CHSH inequality. Our simulations show that DICKA and DIRE protocols employing tripartite Bell inequalities can significantly outperform their bipartite counterparts. Moreover, we establish that genuine multipartite entanglement is not a precondition for multipartite DIRE while its necessity for DICKA remains an open question.

quant-ph↗

arXiv2022

Overcoming fundamental bounds on quantum conference key agreement

Twin-Field Quantum Key Distribution (TF-QKD) enables two distant parties to establish a shared secret key, by interfering weak coherent pulses (WCPs) in an intermediate measuring station. This allows TF-QKD to reach greater distances than traditional QKD schemes and makes it the only scheme capable of beating the repeaterless bound on the bipartite private capacity. Here, we generalize TF-QKD to the multipartite scenario. Specifically, we propose a practical conference key agreement (CKA) protocol that only uses WCPs and linear optics and prove its security with a multiparty decoy-state method. Our protocol allows an arbitrary number of parties to establish a secret conference key by single-photon interference, enabling it to overcome recent bounds on the rate at which conference keys can be established in quantum networks without a repeater.

quant-ph↗

arXiv2022

Predicting hot-electron free energies from ground-state data

Machine-learning potentials are usually trained on the ground-state, Born-Oppenheimer energy surface, which depends exclusively on the atomic positions and not on the simulation temperature. This disregards the effect of thermally-excited electrons, that is important in metals, and essential to the description of warm dense matter. An accurate physical description of these effects requires that the nuclei move on a temperature-dependent electronic free energy. We propose a method to obtain machine-learning predictions of this free energy at an arbitrary electron temperature using exclusively training data from ground-state calculations, avoiding the need to train temperature-dependent potentials, and benchmark it on metallic liquid hydrogen at the conditions of the core of gas giants and brown dwarfs. This work demonstrates the advantages of hybrid schemes that use physical consideration to combine machine-learning predictions, providing a blueprint for the development of similar approaches that extend the reach of atomistic modelling by removing the barrier between physics and data-driven methodologies.

cond-mat.mtrl-sci↗

arXiv2022

Secure Anonymous Conferencing in Quantum Networks

Users of quantum networks can securely communicate via so-called (quantum) conference key agreement --making their identities publicly known. In certain circumstances, however, communicating users demand anonymity. Here, we introduce a security framework for anonymous conference key agreement with different levels of anonymity, which is inspired by the epsilon-security of quantum key distribution. We present efficient and noise-tolerant protocols exploiting multipartite Greenberger-Horne-Zeilinger (GHZ) states and prove their security in the finite-key regime. We analyze the performance of our protocols in noisy and lossy quantum networks and compare with protocols that only use bipartite entanglement to achieve the same functionalities. Our simulations show that GHZ-based protocols can outperform protocols based on bipartite entanglement and that the advantage increases for protocols with stronger anonymity requirements. Our results strongly advocate the use of multipartite entanglement for cryptographic tasks involving several users.

quant-ph↗

arXiv2022

Topology, oxidation states, and charge transport in ionic conductors

Recent theoretical advances, based on a combination of concepts from Thouless' topological theory of adiabatic charge transport and a newly introduced gauge-invariance principle for transport coefficients, have permitted to connect (and reconcile) Faraday's picture of ionic transport -- whereby each atom carries a well-defined integer charge -- with a rigorous quantum description of the electronic charge-density distribution, which hardly suggests its partition into well defined atomic contributions. In this paper we review these progress and in particular that, by relaxing some general topological conditions, charge may be transported in ionic conductors without any net ionic displacements. After reporting numerical experiments which corroborate these findings, we introduce a new connection between our topological picture and the well-known Marcus-Hush theory of electron transfer, which we are able to connect with the topology of adiabatic paths drawn by atomic trajectories. As a significant byproduct, the results reviewed here permit to classify different regimes of ionic transport according to the topological properties of the electronic structure of the conducting material. We finally report on a few recent applications to energy materials and planetary sciences.

cond-mat.mtrl-sci↗

arXiv2022

Investigating finite-size effects in molecular dynamics simulations of ion diffusion, heat transport, and thermal motion in superionic materials

The effects of the finite size of the simulation box in equilibrium molecular dynamics simulations are investigated for prototypical superionic conductors of different types, namely the fluorite-structure materials PbF2, CaF2, and UO2 (type-II), and the α phase of AgI (type I). Largely validated empirical force-fields are employed to run ns-long simulations and extract general trends for several properties, at increasing size and in a wide temperature range. This work shows that, for the considered type-II superionic conductors, the diffusivity dramatically depends on the system size and that the superionic regime is shifted to larger temperatures in smaller cells. Furthermore, only simulations of several hundred atoms are able to capture the experimentally-observed, characteristic change in the activation energy of the diffusion process, occurring at the order-disorder transition to the superionic regime. Finite-size effects on ion diffusion are instead much weaker in α-AgI. The thermal conductivity is found generally smaller for smaller cells, where the temperature-independent (Allen-Feldman) regime is also reached at significantly lower temperatures. The finite-size effects on the thermal motion of the non-mobile ions composing the solid matrix follow the simple law which holds for solids.

cond-mat.mtrl-sci↗

arXiv2021

Temperature- and vacancy-concentration-dependence of heat transport in Li$_3$ClO from multi-method numerical simulations

Despite governing heat management in any realistic device, the microscopic mechanisms of heat transport in all-solid-state electrolytes are poorly known: existing calculations, all based on simplistic semi-empirical models, are unreliable for superionic conductors and largely overestimate their thermal conductivity. In this work, we deploy a combination of state-of-the-art methods to calculate the thermal conductivity of a prototypical Li-ion conductor, the Li$_3$ClO antiperovskite. By leveraging ab initio, machine-learning, and force-field descriptions of inter-atomic forces, we are able to reveal the massive role of anharmonic interactions and diffusive defects on the thermal conductivity and its temperature dependence, and to eventually embed their effects into a simple rationale which is likely applicable to a wide class of ionic conductors.

cond-mat.mtrl-sci↗

arXiv2021

Invariance principles in the theory and computation of transport coefficients

In this work we elaborate on two recently discovered invariance principles, according to which transport coefficients are, to a large extent, independent of the microscopic definition of the densities and currents of the conserved quantities being transported (energy, momentum, mass, charge). The first such principle, gauge invariance, allows one to define a quantum adiabatic energy current from density-functional theory, from which the heat conductivity can be uniquely defined and computed using equilibrium ab initio molecular dynamics. When combined with a novel topological definition of atomic oxidation states, gauge invariance also sheds new light onto the mechanisms of charge transport in ionic conductors. The second principle, convective invariance, allows one to extend the analysis to multi-component systems. These invariance principles can be combined with new spectral analysis methods for the current time series to be fed into the Green-Kubo formula to obtain accurate estimates of transport coefficients from relatively short molecular dynamics simulations.

cond-mat.stat-mech↗

arXiv2021

Experimental quantum conference key agreement

Quantum networks will provide multi-node entanglement over long distances to enable secure communication on a global scale. Traditional quantum communication protocols consume pair-wise entanglement, which is sub-optimal for distributed tasks involving more than two users. Here we demonstrate quantum conference key agreement, a quantum communication protocol that exploits multi-partite entanglement to efficiently create identical keys between N users with up to N-1 rate advantage in constrained networks. We distribute four-photon Greenberger-Horne-Zeilinger (GHZ) states generated by high-brightness, telecom photon-pair sources across up to 50 km of fibre, implementing multi-user error correction and privacy amplification on resulting raw keys. Under finite-key analysis, we establish $1.15\times10^6$ bits of secure key, which are used to encrypt and securely share an image between the four users in a conference transmission. We have demonstrated a new protocol tailored for multi-node networks leveraging low-noise, long-distance transmission of GHZ states that will pave the way forward for future multiparty quantum information processing applications.

quant-ph↗

arXiv2021

Uncertainty estimation for molecular dynamics and sampling

Machine learning models have emerged as a very effective strategy to sidestep time-consuming electronic-structure calculations, enabling accurate simulations of greater size, time scale and complexity. Given the interpolative nature of these models, the reliability of predictions depends on the position in phase space, and it is crucial to obtain an estimate of the error that derives from the finite number of reference structures included during the training of the model. When using a machine-learning potential to sample a finite-temperature ensemble, the uncertainty on individual configurations translates into an error on thermodynamic averages, and provides an indication for the loss of accuracy when the simulation enters a previously unexplored region. Here we discuss how uncertainty quantification can be used, together with a baseline energy model, or a more robust although less accurate interatomic potential, to obtain more resilient simulations and to support active-learning strategies. Furthermore, we introduce an on-the-fly reweighing scheme that makes it possible to estimate the uncertainty in the thermodynamic averages extracted from long trajectories. We present examples covering different types of structural and thermodynamic properties, and systems as diverse as water and liquid gallium.

physics.chem-ph↗