Searcharxiv⌕ Search

arXiv subjects

Ricardo Grau-Crespo

Publications and source records attributed to Ricardo Grau-Crespo.

At least 19 recordsLinked to original sources

Discovery and recovery of crystalline materials with property-conditioned transformers

Generative models have recently shown great promise for accelerating the design and discovery of new functional materials. Conditional generation enhances this capacity by allowing inverse design, where specific desired properties can be requested during the generation process. However, conditioning of transformer-based approaches, in particular, is constrained by discrete tokenisation schemes and the risk of catastrophic forgetting during fine-tuning. This work introduces CrystaLLM-π (property injection), a conditional autoregressive framework that integrates continuous property representations directly into the transformer's attention mechanism. Two architectures, Property-Key-Value (PKV) Prefix attention and PKV Residual attention, are presented. These methods bypass inefficient sequence-level tokenisation and preserve foundational knowledge from unsupervised pre-training on Crystallographic Information Files (CIFs) as textual input. We establish the efficacy of these mechanisms through systematic robustness studies and evaluate the framework's versatility across two distinct tasks. First, for structure recovery, the model processes high-dimensional, heterogeneous X-ray diffraction patterns, achieving structural accuracy competitive with specialised models and demonstrating applications to experimental structure recovery and polymorph differentiation. Second, for materials discovery, the model is fine-tuned on a specialised photovoltaic dataset to generate novel, stable candidates validated by Density Functional Theory (DFT). It implicitly learns to target optimal band gap regions for high photovoltaic efficiency, demonstrating a capability to map complex structure-property relationships. CrystaLLM-π provides a unified, flexible, and computationally efficient framework for inverse materials design.

cond-mat.mtrl-sci↗

Thermodynamic Stability and Hydrogen Bonds in Mixed Halide Perovskites

The stability of mixed halide perovskites against phase separation is crucial for their optoelectronic applications, yet difficult to rationalize due to the interplay of enthalpic, configurational, and dynamical effects. Here we present a simple thermodynamic framework for multicomponent halide perovskites of composition FA$_{1-x}$MA$_{x-y}$Cs$_y$Pb(I$_{1-z}$Br$_z$)$_3$, based on \textit{ab initio} molecular dynamics. By decomposing the free energy of mixing into enthalpic, configurational, and rotational entropic contributions, we show that although the enthalpy of mixing is generally positive, the solid solutions are thermodynamically stable against phase separation due to the large configurational entropy associated with random substitution on cation and halide sublattices. Mixing reduces the rotational entropy of the organic cations, partially offsetting the configurational stabilization. However, within our model, this rotational penalty is not sufficient to overcome the configurational driving force, and a curvature analysis within a regular-solution model does not predict a miscibility gap for any of the mixing channels considered. Analysis of hydrogen-bond dynamics shows that MA--Y (Y = I, Br) interactions are more persistent than FA--Y interactions, while the dominant FA-donated N$-$H$\cdots$I hydrogen bonds remain nearly composition-invariant. Cs-containing mixtures, in which Cs$^{+}$ forms no hydrogen bonds, can nevertheless be thermodynamically stable. These results demonstrate that hydrogen bonding does not control thermodynamic stability in mixed halide perovskites. Instead, phase stability is governed by the balance between strong configurational entropy and a smaller, systematically destabilizing rotational-entropy correction.

cond-mat.mtrl-sci↗

Inversion of the impedance response towards physical parameter extraction using interpretable machine learning

Interpreting the impedance response of perovskite solar cells (PSCs) is challenging due to the complex coupling of ionic and electronic motion. While drift-diffusion (DD) modelling is a reliable method, its mathematical complexity makes directly extracting physical parameters from experimental data infeasible. This work uses DD modelling to generate a large synthetic dataset of impedance spectra for a standard TiO2/MAPI/spiro configuration. This dataset trains machine learning (ML) models to predict recombination and ionic parameters from impedance measurements. A Gradient Boosting Regressor, using features from a generalized equivalent circuit, showed the best performance. Interpretative analysis indicates that open-circuit impedance experiments best probe recombination losses, while short-circuit conditions are more adequate for extracting ionic features like concentrations and mobilities. The trained ML models were tested on experimental spectra, confirming the inferred physical parameters could reproduce the data. For the studied configuration, predicted ion concentrations were (1.3-3.3)e17 cm-3, ion mobilities were (5-7)e-11 cm2V-1s-1, and surface recombination velocities were 7-9 and 23-40 m/s. This approach provides insights into the physical information extractable from impedance measurements and paves the way for ML models to unambiguously derive efficiency-determining parameters for solar cells.

physics.app-ph↗

Crystal Structure Generation with Autoregressive Large Language Modeling

The generation of plausible crystal structures is often the first step in predicting the structure and properties of a material from its chemical composition. Quickly generating and predicting inorganic crystal structures is important for the discovery of new materials, which can target applications such as energy or electronic devices. However, most current methods for crystal structure prediction are computationally expensive, slowing the pace of innovation. Seeding structure prediction algorithms with quality generated candidates can overcome a major bottleneck. Here, we introduce CrystaLLM, a methodology for the versatile generation of crystal structures, based on the autoregressive large language modeling (LLM) of the Crystallographic Information File (CIF) format. Trained on millions of CIF files, CrystaLLM focuses on modeling crystal structures through text. CrystaLLM can produce plausible crystal structures for a wide range of inorganic compounds unseen in training, as demonstrated by ab initio simulations. The integration with predictors of formation energy permits the use of a Monte Carlo Tree Search algorithm to improve the generation of meaningful structures. Our approach challenges conventional representations of crystals, and demonstrates the potential of LLMs for learning effective 'world models' of crystal chemistry, which will lead to accelerated discovery and innovation in materials science.

cond-mat.mtrl-sci↗

Theoretical investigation of the lattice thermal conductivities of II-IV-V2 pnictide semiconductors

Ternary pnictides semiconductors with II-IV-V2 stoichiometry hold potential as cost effective thermoelectric materials with suitable electronic transport properties, but their lattice thermal conductivities ($κ$) are typically too high. Gaining insight into their vibrational properties is therefore crucial to finding strategies to reduce $κ$ and achieve improved thermoelectric performance. We present a theoretical exploration of the lattice thermal conductivities for a set of pnictide semiconductors with ABX2 composition (A = Zn, Cd; B = Si, Ge, Sn; and X = P, As), using machine-learning based regression algorithms to extract force constants from a reduced number of density functional theory simulations, and then solving the Boltzmann transport equation for phonons. Our results align well available experimental data, decreasing the mean absolute error by ~3 Wm-1K-1 with respect to the best previous set of theoretical predictions. Zn-based ternary pnictides have, on average, more than double the thermal conductivity of the Cd-based compounds. Anisotropic behaviour increases with the mass difference between A and B cations, but while the nature of the anion does not affect the structural anisotropy, the thermal conductivity anisotropy is typically higher for arsenides than for phosphides. We identify compounds, like CdGeAs2, for which nanostructuring to an affordable range of particle sizes could lead to values low enough for thermoelectric applications.

cond-mat.mtrl-sci↗

Hydrogen bonds in lead halide perovskites: insights from ab initio molecular dynamics

Hydrogen bonds (HBs) play an important role in the rotational dynamics of organic cations in hybrid organic/inorganic halide perovskites, affecting the structural and electronic properties of the perovskites. However, the properties and even the existence of HBs in these perovskites are not well established. We investigate HBs in perovskites MAPbBr$_3$ (MA$^+$=CH$_3$NH$_3^+$), FAPbI$_3$ (FA$^+$= CH(NH$_2$)$_2^+$), and their solid solution (FAPbI$_3$)$_{7/8}$(MAPbBr$_3$)$_{1/8}$, using ab initio molecular dynamics and electronic structure calculations. We consider HBs donated by X-H fragments (X=N, C) of the organic cations and accepted by the halides (Y=Br, I), and characterize their properties based on pair distribution functions and on a combined distribution function of hydrogen-acceptor distance with donor-hydrogen-acceptor angle. By analyzing these functions, we establish geometric criteria for HB existence based on hydrogen-acceptor distance $d(H-Y)$ and donor-hydrogen-acceptor angle $\measuredangle(X-H-Y)$. The distance condition is defined as $d(H-Y)<0.3$ nm, for N-H-donated HBs, and $d(H-Y)<0.4$ nm for C-H-donated HBs. The angular condition is $135{^\circ}\le\measuredangle(X-H-Y)\le 180{^\circ}$ for both types of HBs. At the simulated temperature (350 K), the HBs dynamically break and form. We compute time correlation functions of HB existence and HB lifetimes, which range between 0.1 and 0.3 picoseconds at that temperature. The analysis of HB lifetimes indicates that N-H--Br bonds are relatively stronger than N-H--I bonds, while C-H--Y bonds are weaker. To evaluate the impact of HBs on vibrational spectra, we present the power spectra, showing that peaks associated with N-H stretching modes in perovskites are redshifted and asymmetrically deformed compared with the peaks of isolated cations.

cond-mat.mtrl-sci↗

Predicting Thermoelectric Transport Properties from Composition with Attention-based Deep Learning

Thermoelectric materials can be used to construct devices which recycle waste heat into electricity. However, the best known thermoelectrics are based on rare, expensive or even toxic elements, which limits their widespread adoption. To enable deployment on global scales, new classes of effective thermoelectrics are thus required. $\textit{Ab initio}$ models of transport properties can help in the design of new thermoelectrics, but they are still too computationally expensive to be solely relied upon for high-throughput screening in the vast chemical space of all possible candidates. Here, we use models constructed with modern machine learning techniques to scan very large areas of inorganic materials space for novel thermoelectrics, using composition as an input. We employ an attention-based deep learning model, trained on data derived from $\textit{ab initio}$ calculations, to predict a material's Seebeck coefficient, electrical conductivity, and power factor over a range of temperatures and $\textit{n}$- or $\textit{p}$-type doping levels, with surprisingly good performance given the simplicity of the input, and with significantly lower computational cost. The results of applying the model to a space of known and hypothetical binary and ternary selenides reveal several materials that may represent promising thermoelectrics. Our study establishes a protocol for composition-based prediction of thermoelectric behaviour that can be easily enhanced as more accurate theoretical or experimental databases become available.

cond-mat.mtrl-sci↗

Co-substituted BiFeO3: electronic, ferroelectric, and thermodynamic properties from first principles

Bismuth ferrite, BiFeO3, is a multiferroic solid that is attracting increasing attention as a potential photocatalytic material, because the ferroelectric polarisation enhances the separation of photogenerated carriers. With the motivation of finding routes to engineer the band gap and the band alignment, while conserving or enhancing the ferroelectric properties, we have investigated the thermodynamic, electronic and ferroelectric properties of BiCoxFe1 xO3 solid solutions, with 0 < x < 0.13, using density functional theory. We show that the band gap can be reduced from 2.9 eV to 2.1 eV by cobalt substitution, while simultaneously increasing the spontaneous polarisation, which is associated with a notably larger Born effective charge of Co compared to Fe cations. We discuss the interaction between Co impurities, which is strongly attractive and would drive the aggregation of Co, as evidenced by Monte Carlo simulations. Phase separation into a Co-rich phase is therefore predicted to be thermodynamically preferred, and the homogeneous solid solution can only exist in metastable form, protected by slow cation diffusion kinetics. Finally, we discuss the band alignment of pure and Co-substituted BiFeO3 with relevant redox potentials, in the context of its applicability in photocatalysis.

cond-mat.mtrl-sci↗

Spinel nitride solid solutions: charting properties in the configurational space with explainable machine learning

Ab initio prediction of the variation of properties in the configurational space of solid solutions is computationally very demanding. We present an approach to accelerate these predictions via a combination of density functional theory and machine learning, using the cubic spinel nitride GeSn$_2$N$_4$ as a case study, exploring how formation energy and electronic bandgap are affected by configurational variations. Furthermore, we demonstrate the utility of applying explainable machine learning to understand the crystal chemistry origins of the trends that we observe. Different configuration descriptors (Coulomb matrix eigenspectrum, many-body tensor representation, and cluster correlation function vectors) are combined with different models (linear regression, gradient-boosted decision tree, and multi-layer perceptron) to extrapolate the calculation of ab initio properties from a small set of configurations to the full space with thousands of configurations. We discuss the performance of different descriptors and models. SHAP (SHapley Additive exPlanations) analysis of the machine learning models highlights how values of formation energy are dominated by variations in local crystal structure (single polyhedral environments), while values of electronic bandgap are dominated by variations in more extended structural motifs. Finally, we demonstrate the usefulness of this approach by constructing structure-property maps, identifying important configurations of GeSn$_2$N$_4$ with extremal properties, as well as by calculating accurate equilibrium properties using configurational averaging.

cond-mat.mtrl-sci↗

Mixed-anion mixed-cation perovskite (FAPbI$_3$)$_{0.875}$(MAPbBr$_3$)$_{0.125}$: an ab-initio molecular dynamics study

Mixed-anion mixed-cation perovskites with (FAPbI$_3$)$_{1-x}$(MAPbBr$_3$)$_x$ composition have allowed record efficiencies in photovoltaic solar cells, but their atomic-scale behaviour is not well understood yet, in part because their theoretical modelling requires consideration of complex and interrelated dynamic and disordering effects. We present here an ab initio molecular dynamics investigation of the structural, thermodynamic, and electronic properties of the (FAPbI$_3$)$_{0.875}$(MAPbBr$_3$)$_{0.125}$ perovskite. A special quasi-random structure is proposed to mimic the disorder of both the molecular cations and the halide anions, in a stoichiometry that is close to that of one of today's most efficient perovskite solar cells. We show that the rotation of the organic cations is more strongly hindered in the mixed structure in comparison with the pure compounds. Our analysis suggests that this mixed perovskite is thermodynamically stable against phase separation despite the endothermic mixing enthalpy, due to the large configurational entropy. The electronic properties are investigated by hybrid density functional calculations including spin-orbit coupling in carefully selected representative configurations extracted from the molecular dynamics. Our model, that is validated here against experimental information, provides a more sophisticated understanding of the interplay between dynamic and disordering effects in this important family of photovoltaic materials.

cond-mat.mtrl-sci↗

Distributed Representations of Atoms and Materials for Machine Learning

The use of machine learning is becoming increasingly common in computational materials science. To build effective models of the chemistry of materials, useful machine-based representations of atoms and their compounds are required. We derive distributed representations of compounds from their chemical formulas only, via pooling operations of distributed representations of atoms. These compound representations are evaluated on ten different tasks, such as the prediction of formation energy and band gap, and are found to be competitive with existing benchmarks that make use of structure, and even superior in cases where only composition is available. Finally, we introduce a new approach for learning distributed representations of atoms, named SkipAtom, which makes use of the growing information in materials structure databases.

cond-mat.mtrl-sci↗

Engineering the electronic and optical properties of 2D porphyrin paddlewheel metal-organic frameworks

Metal organic frameworks (MOFs) are promising photocatalytic materials due to their high surface area and tuneability of their electronic structure. We discuss here how to engineer the band structures and optical properties of a family of two-dimensional (2D) porphyrin-based MOFs, consisting of M tetrakis(4 carboxyphenyl)porphyrin structures (M TCPP, where M = Zn2+ or Co2+) and metal (Co2+, Ni2+, Cu2+ or Zn2+) paddlewheel clusters, with the aim of optimising their photocatalytic behaviour in solar fuel synthesis reactions (water splitting and/or CO2 reduction). Based on density functional theory (DFT) and time-dependent DFT simulations with a hybrid functional, we studied three types of composition/structural modifications: a) varying the metal centre at the paddlewheel or at the porphyrin centre to modify the band alignment; b) partially reducing the porphyrin unit to chlorin, which leads to stronger absorption of visible light; and c) substituting the benzene bridging between the porphyrin and paddlewheel, by ethyne or butadiyne bridges, with the aim of modifying the linker to metal charge transfer behaviour. Our work offers new insights on how to improve the photocatalytic behaviour of porphyrin- and paddlewheel-based MOFs.

cond-mat.mtrl-sci↗

Electron and phonon interactions and transport in ultra-high-temperature ceramic ZrC

We have simulated the ultra-high-temperature ceramic zirconium carbide (ZrC) in order to predict electron and phonon scattering properties, including lifetimes and transport. Our predictions of heat and charge conductivity, which extend to 3000 K, are relevant to extreme temperature applications of ZrC. Mechanisms are identified on a first principles basis that considerably enhance or suppress heat transport at high temperature, including strain and anharmonicity. The extent to which boundary confinement and isotope scattering effects lower thermal conductivity is predicted.

cond-mat.mtrl-sci↗

The origin of the vanadium dioxide transition entropy

The reversible metal-insulator transition in VO$_2$ at $T_\text{C} \approx 340$ K has been closely scrutinized yet its thermodynamic origin remains ambiguous. We discuss the origin of the transition entropy by calculating the electron and phonon contributions at $T_\text{C}$ using density functional theory. The vibration frequencies are obtained from harmonic phonon calculations, with the soft modes that are imaginary at zero temperature renormalized to real values at $T_\text{C}$ using experimental information from diffuse x-ray scattering at high-symmetry wavevectors. Gaussian Process Regression is used to infer the transformed frequencies for wavevectors across the whole Brillouin zone, and in turn compute the finite temperature phonon partition function to predict transition thermodynamics. Using this method, we predict the phase transition in VO$_2$ is driven five to one by phonon entropy over electronic entropy, and predict a total transition entropy that accounts for $95$ % of the calorimetric value.

cond-mat.mtrl-sci↗

Mixing thermodynamics and photocatalytic properties of GaP-ZnS solid solutions

Preparation of solid solutions represents an effective means to improve the photocatalytic properties of semiconductor-based materials. Nevertheless, the effects of site-occupancy disorder on the mixing stability and electronic properties of the resulting compounds are difficult to predict and consequently many experimental trials may be required before achieving enhanced photocatalytic activity. Here, we employ first-principles methods based on density functional theory to estimate the mixing free energy and the structural and electronic properties of (GaP)$_{x}$(ZnS)$_{1-x}$ solid solutions, a representative semiconductor-based optoelectronic material. Our method relies on a multi-configurational supercell approach that takes into account the configurational and vibrational contributions to the free energy. Phase competition among the zinc-blende and wurtzite polymorphs is also considered. We demonstrate overall excellent agreement with the available experimental data: (1)~zinc-blende emerges as the energetically most favorable phase, (2)~the solid solution energy band gap lies within the $2$--$3$~eV range for all compositions, and (3)~the energy band gap of the solid solution is direct for compositions $x \le 75$\%. We find that at ambient conditions most (GaP)$_{x}$(ZnS)$_{1-x}$ solid solutions are slightly unstable against decomposition into GaP- and ZnS-rich regions. Nevertheless, compositions $x \approx 25$, 50, and 75\% render robust metastable states that owing to their favorable energy band gaps and band levels relative to vacuum are promising hydrogen evolution photocatalysts for water splitting under visible light. The employed theoretical approach provides valuable insights into the physicochemical properties of potential solid-solution photocatalysts and offers useful guides for their experimental realization.

cond-mat.mtrl-sci↗

Origin of the monolayer Raman signature in hexagonal boron nitride: a first-principles analysis

Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It is clear that a small in-plane contraction can explain the Raman peak upshift from bulk to monolayer. However, we show that the larger in-plane parameter in the bulk (compared to the monolayer) results from non-local correlation effects, which cannot be accounted for by local functionals or those with empirical dispersion corrections. Using a non-local-correlation functional, we then investigate the effect of finite temperatures on the Raman signature. We demonstrate that bulk h-BN thermally expands in the direction perpendicular to the layers, while the intralayer distances slightly contract, in agreement with observed experimental behavior. Interestingly, the difference in in-plane cell parameter between bulk and monolayer decreases with temperature, and becomes very small at room temperature. We conclude that the different thermal expansion of bulk and monolayer partially "erases" the intrinsic Raman signature, accounting for its small magnitude in recent experiments on suspended samples.

cond-mat.mtrl-sci↗

First-principles study of the inversion thermodynamics and electronic structure of Fe$M_2X_4$ (thio)spinels ($M=$ Cr, Mn, Co, Ni; $X=$ O, S)

Fe$M_2X_4$ spinels, where $M$ is a transition metal and $X$ is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for $M=$ Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+$U$). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr$_2X_4$ and FeMn$_2$S$_4$ are fully normal, FeNi$_2X_4$ and FeCo$_2$S$_4$ are intermediate, and FeCo$_2$O$_4$ and FeMn$_2$O$_4$ are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr$_2X_4$, FeMn$_2X_4$, FeCo$_2$O$_4$ and FeNi$_2$O$_4$ are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When $M$ is filling the tetrahedral positions, the Cr-containing compounds and FeMn$_2$O$_4$ are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn$_2$S$_4$. Our calculations suggest that the spin filtering properties of the Fe$M_2X_4$ (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

cond-mat.mtrl-sci↗

Crystal structure of cobalt hydroxide carbonate Co$_2$CO$_3$(OH)$_2$: density functional theory and X-ray diffraction investigation

We have investigated the structure of Co$_2$CO$_3$(OH)$_2$ using Density Functional Theory (DFT) simulations as well as Powder X-Ray Diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. We consider two possible monoclinic phases, with closely related but symmetrically different crystal structures, based on those of the minerals malachite and rosasite, as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite. Our DFT simulations predict that the rosasite-like and the malachite-like phases are two different local minima of the potential energy landscape for Co$_2$CO$_3$(OH)$_2$, and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model (monoclinic with space group P1121/n and cell parameters a = 3.1408(4) Å, b = 12.2914(17) Å, c = 9.3311(16) Å, $γ$ = 82.299(16)$^{\circ}$). However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. We discuss the relationship between the rosasite and malachite phases of Co$_2$CO$_3$(OH)$_2$ and show that they can be seen as polytypes. Based on the similar calculated stability of these two polytypes, we speculate that some level of stacking disorder could account for the poor fit of our PXRD data. The possibility that Co$_2$CO$_3$(OH)$_2$ could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.

cond-mat.mtrl-sci↗