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Mariana Rossi

Publications and source records attributed to Mariana Rossi.

At least 19 recordsLinked to original sources

High-quality, high-information datasets for universal atomistic machine learning

The quality, consistency, and information content of training data is often what determines the practical value of machine-learning models for atomistic simulations. Yet, many widely used electronic-structure databases are assembled having materials screening as primary goal rather than robust force-field learning, are limited in their scope to a specific class of chemical compounds, and/or employ inconsistent DFT functionals and settings. Here we introduce MAD-1.6, a highly curated dataset designed explicitly for training broadly applicable atomistic models across the periodic table at high levels of theory. MAD-1.6 extends the MAD dataset with targeted enrichment strategies that improve the coverage of chemical space to 102 elements while keeping the total number of configurations compact. All structures are computed with a single, standardized all-electron DFT workflow using the r$^2$SCAN meta-GGA functional and consistent convergence settings, ensuring uniformity across chemically heterogeneous systems. The dataset encompasses molecules, clusters, bulk crystals, surfaces, and low-dimensional structures, and its quality and consistency are further enhanced by outlier removal using uncertainty quantification. We demonstrate the high accuracy that can be achieved with the proposed dataset by training PET-MAD-1.6, a generally applicable r$^2$SCAN interatomic potential that covers 102 elements in the periodic table and achieves exceptional levels of benchmark accuracy and stability in challenging simulation protocols.

cond-mat.mtrl-sci

SALTED: a symmetry-adapted machine-learning program for predicting electron-densities in molecules and materials

SALTED provides an open-source Python package for machine learning the quantum-mechanical electron density, $n(\mathbf{r})$, in molecular and condensed-phase systems based on input atomic coordinates and species. The program adopts a linear atom-centered decomposition of the electron density, which makes it highly transferable across diverse atomistic configurations sharing similar chemical environments. Because of this representation choice, SALTED is naturally interfaced with state-of-the-art electronic-structure programs based on atomic orbitals, namely CP2K, FHI-aims, and PySCF, from which reference electron-density data can be generated and used to train a model. The learning algorithm is based on a symmetry-adapted extension of Gaussian process regression, making SALTED especially efficient in small-data regimes. Thanks to the implementation of vector-field kernel functions, SALTED can also learn the first-order response of the electron density to applied electric fields, $\partial n(\mathbf{r})/\partial \mathbf{E}$. The application of SALTED within computational workflows has already shown its utility in a wide variety of contexts, including the calculation of polarization vectors and polarizability tensors, the accurate evaluation of Coulomb forces in QM/MM molecular-dynamics simulations, and electronic-structure studies of large-scale 2D materials.

cond-mat.mtrl-sci

Long-Range Machine Learning of Electron Density for Twisted Bilayer Moiré Materials

Moiré superlattices in two-dimensional (2D) materials exhibit rich quantum phenomena, but ab initio modelling of these systems remains computationally prohibitive. Existing machine learning methods for accelerating density-functional theory (DFT) can target the prediction of different quantities and often rely on the locality assumption. Here we train a Gaussian process regression SALTED model exclusively on the electron densities of small displaced bilayer structures and then extrapolate electron density prediction to the large supercells required to describe small twist angles between these bilayers. We show the necessity of long-range descriptors to yield reliable band structures and electrostatic properties of large twisted bilayer structures, when these are derived from predicted densities. We demonstrate that the choice of descriptor determines the distribution of residual density errors, which in turn affects the downstream electronic properties. We apply our models to twisted bilayer graphene, hexagonal boron nitride, and transition metal dichalcogenides, focusing on the model's capacity to predict complex phenomena, including flat band formation, bandwidth narrowing, domain-wall electric fields, and spin-orbit coupling effects. Beyond moiré materials, this approach provides a general methodology for electronic structure prediction in large-scale systems with substantial long-range phenomena related to non-local geometric information.

cond-mat.mtrl-sci

Dyna-Mat: End-to-end benchmarking of foundation machine learning interatomic potentials in finite-temperature ensembles

Foundation machine learning interatomic potentials (MLIPs) are increasingly being used as drop-in replacements for first-principles calculations, enabling simulations of materials at length and time scales that were previously inaccessible. However, due to lack of ground truth data, their accuracy on structural and dynamical observables in finite thermodynamic ensembles is yet to be established. Here, we introduce Dyna-Mat-v1.0, a benchmark dataset of condensed-phase first-principles molecular dynamics trajectories designed to test foundation MLIPs at realistic finite-temperature conditions. Using this dataset, we evaluate 15 foundation MLIPs across four model tiers by comparing both single-point energy and force errors on first-principles configurations and observables generated from MLIP-driven trajectories. We find that "on average" models with lower single-point force errors also yield lower errors for structural and dynamical observables. However, there are individual systems for which low force errors lead to qualitative failures in the predicted structure. Pressure remains poorly described across most models, pointing to limitations in the density functional theory stress labels available in current large-scale training datasets. Finally, we construct an accuracy-cost Pareto frontier to identify the best trade-offs for molecular dynamics with foundation MLIPs, finding that the latest generation of cross-trained models is close to Pareto-optimal according to the accuracy metrics considered here. Overall, Dyna-Mat-v1.0 shows that end-to-end finite-temperature validation is essential for quantifying the predictive behaviour of foundation MLIPs, and provides a simple, scalable route for assessing them beyond static and harmonic benchmarks relevant to materials design.

cond-mat.mtrl-sci

Accurate Machine Learning Interatomic Potentials for Polyacene Molecular Crystals: Application to Single Molecule Host-Guest Systems

Emerging machine learning interatomic potentials (MLIPs) offer a promising solution for large-scale accurate material simulations, but stringent tests related to the description of vibrational dynamics in molecular crystals remain scarce. Here, we develop a general MLIP by leveraging the graph neural network-based MACE architecture and active-learning strategies to accurately capture vibrational dynamics across a range of polyacene-based molecular crystals, namely naphthalene, anthracene, tetracene and pentacene. Through careful error propagation, we show that these potentials are accurate and enable the study of anharmonic vibrational features, vibrational lifetimes, and vibrational coupling. In particular, we investigate large-scale host-guest systems based on these molecular crystals, showing the capacity of molecular-dynamics-based techniques to explain and quantify vibrational coupling between host and guest nuclear motion. Our results establish a framework for understanding vibrational signatures in large-scale complex molecular systems and thus represent an important step for engineering vibrational interactions in molecular environments.

cond-mat.mtrl-sci

Perspective: Towards sustainable exploration of chemical spaces with machine learning

Artificial intelligence is transforming molecular and materials science, but its growing computational and data demands raise critical sustainability challenges. In this Perspective, we examine resource considerations across the AI-driven discovery pipeline--from quantum-mechanical (QM) data generation and model training to automated, self-driving research workflows--building on discussions from the ``SusML workshop: Towards sustainable exploration of chemical spaces with machine learning'' held in Dresden, Germany. In this context, the availability of large quantum datasets has enabled rigorous benchmarking and rapid methodological progress, while also incurring substantial energy and infrastructure costs. We highlight emerging strategies to enhance efficiency, including general-purpose machine learning (ML) models, multi-fidelity approaches, model distillation, and active learning. Moreover, incorporating physics-based constraints within hierarchical workflows, where fast ML surrogates are applied broadly and high-accuracy QM methods are used selectively, can further optimize resource use without compromising reliability. Equally important is bridging the gap between idealized computational predictions and real-world conditions by accounting for synthesizability and multi-objective design criteria, which is essential for practical impact. Finally, we argue that sustainable progress will rely on open data and models, reusable workflows, and domain-specific AI systems that maximize scientific value per unit of computation, enabling efficient and responsible discovery of technological materials and therapeutics.

cs.LG

Path Integral Methods in Atomistic Modelling: An Introduction

This book provides an introduction to path integral methods and their application to modeling atomistic processes. The book covers both the foundational theory and recently developed simulation techniques. The text provides a self-contained resource and was originally developed for the CECAM schools on Path Integral Methods.

physics.chem-ph

Moiré-induced symmetry breaking of charge order in van der Waals heterostructures

Layered materials that stack different lattice symmetries are rare in nature. Misfit layered chalcogenides, which combine square and hexagonal lattices of rocksalt monochalcogenides and transition-metal dichalcogenides, provide a platform to explore how incommensurability and explicit symmetry breaking impact collective electronic phases. Here we use low-temperature scanning tunneling microscopy/spectroscopy to probe the misfit compounds (MS)$_{1+δ}$TaS$_{2}$ with M = Pb, Sn and track how the misfit interface reshapes the electronic ground state of the embedded 1H-TaS$_{2}$ monolayers. High-resolution STM imaging and Fourier analysis reveal that the charge-density wave (CDW) is incommensurate and fragments into nanometer-sized domains. Strikingly, the CDW exhibits a pronounced and anisotropic response to the uniaxial moiré potential imposed by the misfit layer: its coherence lengths and ordering wavevectors become inequivalent, demonstrating a strong nonlinear coupling between the intrinsic CDW instability and the symmetry-breaking moiré field. First-principles-informed multiscale modeling shows that this reorganization arises from the combined effect of interlayer charge transfer and the spatially anisotropic energy landscape introduced by the misfit interface. In contrast, superconductivity is comparatively insensitive to the moiré, revealing a uniform, single full-gap consistent with s-wave pairing. Our results establish heterosymmetry stacking as a route to engineer correlated states in van der Waals materials.

cond-mat.str-el

Investigating Anharmonicities in Polarization-Orientation Raman Spectra of Acene Crystals with Machine Learning

We present a first-principles machine-learning computational framework to investigate anharmonic effects in polarization-orientation (PO) Raman spectra of molecular crystals, focusing on anthracene and naphthalene. By combining machine learning models for interatomic potentials and polarizability tensors, we enable efficient, large-scale simulations that capture temperature-dependent vibrational dynamics beyond the harmonic approximation. Our approach reproduces key qualitative features observed experimentally. We show, systematically, what are the fingerprints of anharmonic lattice dynamics, thermal expansion, and Raman tensor symmetries on PO-Raman intensities. However, we find that the simulated polarization dependence of Raman intensities shows only subtle deviations from quasi-harmonic predictions, failing to capture the pronounced temperature-dependent changes that have been reported experimentally in anthracene. We propose that part of these inconsistencies stem from the impossibility to deconvolute certain vibrational peaks when only experimental data is available. This work therefore provides a foundation to improve the interpretation of PO-Raman experiments in complex molecular crystals with the aid of theoretical simulations.

cond-mat.mtrl-sci

Vibrational Spectra of Materials and Molecules from Partially-Adiabatic Elevated-Temperature Centroid Molecular Dynamics

Centroid molecular dynamics (CMD) incorporates nuclear quantum statistics into the calculation of vibrational spectra. However, when performed in Cartesian coordinates, CMD shows unphysical artifacts in certain vibrational bands, known as the curvature problem. Recent work showed that CMD spectra can be freed from the curvature problem by evolving the ring-polymer centroid on a potential of mean force (PMF) calculated at an elevated temperature ($T_e$-CMD). Here we present a partially-adiabatic implementation of $T_e$-CMD (PA-$T_e$-CMD), which eliminates the need for precomputed PMFs and instead yields the centroid force 'on the fly'. We introduce a two-temperature path-integral Langevin thermostat to achieve a temperature separation between centroid and internal modes of the ring polymer. Because it is paramount that the elevated temperature be chosen as low as possible for a given physical temperature in this formulation, we present a general scheme for its determination. We benchmark PA-$T_e$-CMD against exact vibrational spectra for the isolated water monomer and discuss its performance for challenging anharmonic systems: the carbonic acid fluoride molecule (CAF) and the methylammonium lead iodide perovskite (MAPI). We conclude that PA-$T_e$-CMD mitigates the curvature problem and the steep increase in computational cost with decreasing temperature of conventional path-integral methods. We observe energy leakage from the hot internal modes to high-frequency centroid modes in some cases, which, nevertheless, only compromises the spectral lineshapes at lower temperatures. While an adiabatic setup based on a coarse-grained centroid PMF is still preferable when a good pre-trained PMF can be easily obtained, PA-$T_e$-CMD presents a low-barrier single-shot setup for any system.

physics.chem-ph

aims-PAX: Parallel Active eXploration for the automated construction of Machine Learning Force Fields

Recent advances in machine learning force fields (MLFF) have significantly extended the reach of atomistic simulations. Continuous progress in this field requires reliable reference datasets, accurate MLFF architectures, and efficient active learning strategies to enable robust modeling of complex molecular and material systems. Here we introduce aims-PAX, an expedited, multi-trajectory active learning framework that streamlines the development of stable and accurate MLFFs. Designed for a wide range of researchers, aims-PAX offers a modular, high-performance workflow that couples diversified sampling with scalable training across CPU and GPU architectures. Integrated with the widely used ab initio code FHI-aims, the framework supports state-of-the-art ML models and dataset generation using general-purpose (or "foundational") force-fields for rapid deployment in diverse systems. We demonstrate the capabilities of aims-PAX in various challenging tasks: creating datasets and models for highly flexible peptides, multiple organic molecules at once, explicitly solvated molecules, and for efficiently handling computationally demanding systems such as the CsPbI$_3$ perovskite. We show that aims-PAX achieves a reduction of up to three orders of magnitude in the number of required reference calculations, automatically selects challenging systems within a given chemical space, facilitates simulation of solvated molecules with more than thousand atoms, while enabling a ten-fold speedup in active-learning time through optimized resource utilization. This positions aims-PAX as a powerful and versatile platform for next-generation atomistic simulations in both academic and industrial settings.

physics.chem-ph

Attosecond-resolved probing of recolliding electron wave packets in liquids and aqueous solutions

High-harmonic spectroscopy (HHS) in liquids promises real-time access to ultrafast electronic dynamics in the native environment of chemical and biological processes. While electron recollision has been established as the dominant mechanism of high-harmonic generation (HHG) in liquids, resolving the underlying electron dynamics has remained elusive. Here we demonstrate attosecond-resolved measurements of recolliding electron wave packets, extending HHS from neat liquids to aqueous solutions. Using phase-controlled two-colour fields, we observe a linear scaling of the two-colour delay that maximizes even-harmonic emission with photon energy, yielding slopes of 208+/-55 as/eV in ethanol and 124+/-42 as/eV in water, the latter matching ab initio simulations (125+/-48 as/eV). In aqueous salt solutions, we uncover interference minima whose appearance depends on solute type and concentration, arising from destructive interference between solute and solvent emission. By measuring the relative phase of solvent and solute HHG, we retrieve a variation of electron transit time by 113+/-32 as/eV, consistent with our neat-liquid results. These findings establish HHS as a powerful attosecond-resolved probe of electron dynamics in disordered media, opening transformative opportunities for studying ultrafast processes such as energy transfer, charge migration, and proton dynamics in liquids and solutions.

physics.chem-ph

Explaining Principles of Tip-Enhanced Raman Images with Ab Initio Modeling

Tip-enhanced Raman spectroscopy (TERS) is a powerful method for imaging vibrational motion and chemically characterizing surface-bound systems. Theoretical simulations of TERS images often consider systems in isolation, ignoring any substrate support, such as metallic surfaces. Here, we show that this omission leads to deviations from experimentally measured data through simulations with a new finite-field formulation of first-principles simulation of TERS spectra that can address extended, periodic systems. We show that TERS images of tetracyanoethylene on Ag(100) and defective MoS$_2$ monolayers calculated using isolated molecules or cluster models are qualitatively different from those calculated when accounting for the periodicity of the substrate. For Mg(II)-porphine on Ag(100), a system for which a direct experimental comparison is possible, these simulations prove to be crucial for explaining the spatial variation of TERS intensity patterns and allow us to uncover fundamental principles of TERS spectroscopy. We explain how and why surface interactions affect images of out-of-plane vibrational modes much more than those of in-plane modes, providing an important tool for the future interpretation of these images in more complex systems.

cond-mat.mtrl-sci

Electric-Field Driven Nuclear Dynamics of Liquids and Solids from a Multi-Valued Machine-Learned Dipolar Model

The driving of vibrational motion by external electric fields is a topic of continued interest, due to the possibility of assessing new or metastable material phases with desirable properties. Here, we combine ab initio molecular dynamics within the electric-dipole approximation with machine-learning neural networks (NNs) to develop a general, efficient and accurate method to perform electric-field-driven nuclear dynamics for molecules, solids, and liquids. We train equivariant and autodifferentiable NNs for the interatomic potential and the dipole, modifying the model infrastructure to account for the multi-valued nature of the latter in periodic systems. We showcase the method by addressing property modifications induced by electric field interactions in a polar liquid and a polar solid from nanosecond-long molecular dynamics simulations with quantum-mechanical accuracy. For liquid water, we present a calculation of the dielectric function in the GHz to THz range and the electrofreezing transition, showing that nuclear quantum effects enhance this phenomenon. For the ferroelectric perovskite LiNbO$_3$, we simulate the ferroelectric to paraelectric phase transition and the non-equilibrium dynamics of driven phonon modes related to the polarization switching mechanisms, showing that a full polarization switch is not achieved in the simulations.

cond-mat.mtrl-sci

Multi-plateau high-harmonic generation in liquids driven by off-site recombination

Non-perturbative high-harmonic generation (HHG) has recently been observed in the liquid phase, where it was demonstrated to have a different physical mechanism compared to gas and solid phases of matter. The currently best physical picture for liquid HHG eliminates scattered-electron contributions and identifies on-site recombination as the dominant contributor. This mechanism accurately predicts the cut-off energy and its independence of the driving laser wavelength and intensity. However, this implies that additional energy absorbed in the liquid as the driving laser intensity is increased does not result in higher-order non-linearities, which is in contrast to the conventional expectation from most nonlinear media. Here we experimentally observe the formation of a second plateau in HHG from multiple liquids (water, heavy water, propranol, and ethanol), thus explaining the conundrum of the missing higher-order response. We analyze this second plateau with a combination of experimental, state-of-the-art ab-initio numerical (in diverse systems of water, ammonia, and liquid methane), and semi-classical analytical, techniques, and elucidate its physical origin to electrons that recombine on neighboring water molecules rather than at the ionization site, leading to unique HHG ellipticity dependence. Remarkably, we find that the second plateau is dominated by electrons recombining at the second solvation shell, relying on wide hole delocalization. Theory also predicts the appearance of even higher plateaus, indicating a general trend. Our work establishes new physical phenomena in the highly non-linear optical response of liquids, paving the way to attosecond probing of electron dynamics in solutions.

physics.chem-ph

Picocavity-Enhanced Raman Spectroscopy of Physisorbed H$_2$ and D$_2$ Molecules

We report on tip-enhanced Raman spectroscopy of H2 and D2 molecules physisorbed within a plasmonic picocavity at 10 K. The intense Raman peaks resulting from the rotational and vibrational transitions are observed at subnanometer gap distances of the junction formed by an Ag tip and an Ag(111) surface, where a picocavity-enhanced field plays a crucial role. A significant redshift of the H-H stretch frequency is observed as the gap distance decreases, while the D-D stretch frequency is unaffected. Density functional theory, path-integral molecular dynamics, and quantum anharmonic vibrational energy calculations suggest that this unexpected isotope effect is explained by a different molecular density between H2 and D2 on the surface.

physics.optics

Hexagonal ice density dependence on inter atomic distance changes due to nuclear quantum effects

Hexagonal ice ($\rm{I_h}$), the most common structure of ice, displays a variety of fascinating properties. Despite major efforts, a theoretical description of all its properties is still lacking. In particular, correctly accounting for its density and interatomic interactions is of utmost importance as a stepping stone for a deeper understanding of other properties. Deep potentials are a recent alternative to investigate the properties of {\iceIH}, which aims to match the accuracy of \textit{ab initio} simulations with the simplicity and scalability of classical molecular dynamics. This becomes particularly significant if one wishes to address nuclear quantum effects. In this work, we use machine learning potentials obtained for different exchange and correlation functionals to simulate the structural and vibrational properties of {\iceIH}. We show that most functionals overestimate the density of ice compared to experimental results. Furthermore, a quantum treatment of the nuclei leads to even further distancing from experiments. We understand this by highlighting how different inter-atomic interactions play a role in obtaining the equilibrium density. In particular, different from water clusters and bulk water, nuclear quantum effects lead to stronger H-bonds in {\iceIH}.

cond-mat.mtrl-sci

Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction

We address the challenge of incorporating non-Markovian electronic friction effects in quantum-mechanical approximations of dynamical observables. A generalized Langevin equation (GLE) is formulated for ring-polymer molecular dynamics (RPMD) rate calculations, which combines electronic friction with a description of nuclear quantum effects (NQEs) for adsorbates on metal surfaces. An efficient propagation algorithm is introduced that captures both the spatial dependence of friction strength and non-Markovian frictional memory. This framework is applied to a model of hydrogen diffusing on Cu(111) derived from ab initio density functional theory (DFT) calculations, revealing significant alterations in rate constants and tunnelling crossover temperatures due to non-Markovian effects. Our findings explain why previous classical molecular dynamics simulations with Markovian friction showed unexpectedly good agreement with experiment, highlighting the critical role of non-Markovian effects in first-principles atomistic simulations.

cond-mat.mtrl-sci