Staff directory José Miguel Alonso Pruneda

José Miguel Alonso Pruneda

CSIC Tenured Scientist
Theory and Simulation



  • Atomically Sharp Lateral Superlattice Heterojunctions Built-In Nitrogen-Doped Nanoporous Graphene

    Tenorio M., Moreno C., Febrer P., Castro-Esteban J., Ordejón P., Peña D., Pruneda M., Mugarza A. Advanced Materials; 34 (20, 2110099) 2022. 10.1002/adma.202110099. IF: 30.849

    Nanometer scale lateral heterostructures with atomically sharp band discontinuities can be conceived as the 2D analogues of vertical Van der Waals heterostructures, where pristine properties of each component coexist with interfacial phenomena that result in a variety of exotic quantum phenomena. However, despite considerable advances in the fabrication of lateral heterostructures, controlling their covalent interfaces and band discontinuities with atomic precision, scaling down components and producing periodic, lattice-coherent superlattices still represent major challenges. Here, a synthetic strategy to fabricate nanometer scale, coherent lateral superlattice heterojunctions with atomically sharp band discontinuity is reported. By merging interdigitated arrays of different types of graphene nanoribbons by means of a novel on-surface reaction, superlattices of 1D, and chemically heterogeneous nanoporous junctions are obtained. The latter host subnanometer quantum dipoles and tunneling in-gap states, altogether expected to promote interfacial phenomena such as interribbon excitons or selective photocatalysis. © 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.

  • Competition between Ta-Ta and Te-Te bonding leading to the commensurate charge density wave in TaTe4

    Guster B., Pruneda M., Ordejón P., Canadell E. Physical Review B; 105 (6, 064107) 2022. 10.1103/PhysRevB.105.064107. IF: 4.036

    The origin of the charge density wave in TaTe4 is discussed on the basis of a first-principles density functional theory analysis of the Fermi surface, electron-hole response function, phonon band structure of the average structure, and structural optimization of the modulated phase. Analysis of the band structure and Fermi surface of the average structure clearly proves that despite the presence of TaTe4 chains in the crystal structure, TaTe4 is in fact a 3D material as far as the electronic structure near the Fermi level is concerned. A Fermi surface nesting mechanism is dismissed as the origin of the 2a×2a×3c structural modulation. The optimized 2a×2a×3c structure, which is found to be the more stable modulation in agreement with the experimental observations, can be obtained directly from a soft-phonon mode computed for the undistorted structure. Our results suggest that the driving force for the distortion is the maximization of Ta-Ta metal-metal bonding subject to inducing the minimum bonding decrease in the Te sublattice. © 2022 American Physical Society.

  • Dynamic control of octahedral rotation in perovskites by defect engineering

    Jia J., He X., Akhtar A., Herranz G., Pruneda M. Physical Review B; 105 (22, 224112) 2022. 10.1103/PhysRevB.105.224112.

    Engineering oxygen octahedra rotation patterns in ABO3 perovskites is a powerful route to design functional materials. Here we propose a strategy that exploits point defects that create local electric dipoles and couple to the oxygen sublattice, enabling direct actuation on the rotational degrees of freedom. This approach, which relies on substituting an A site with a smaller ion, paves a way to couple dynamically octahedra rotations to external electric fields. A common antisite defect, AlLa, in rhombohedral LaAlO3 is taken as a prototype to validate the idea, with atomistic density functional theory calculations supported with an effective lattice model to simulate the dynamics of switching of the local rotational degrees of freedom to long distances. Our simulations provide an insight of the main parameters that govern the operation of the proposed mechanism, and allow to define guidelines for screening other systems where this approach could be used for tuning the properties of the host material. © 2022 American Physical Society.

  • The elphbolt ab initio solver for the coupled electron-phonon Boltzmann transport equations

    Protik N.H., Li C., Pruneda M., Broido D., Ordejón P. npj Computational Materials; 8 (1, 28) 2022. 10.1038/s41524-022-00710-0. IF: 12.241

    elphbolt is a modern Fortran (2018 standard) code for efficiently solving the coupled electron–phonon Boltzmann transport equations from first principles. Using results from density functional and density functional perturbation theory as inputs, it can calculate the effect of the non-equilibrium phonons on the electronic transport (phonon drag) and non-equilibrium electrons on the phononic transport (electron drag) in a fully self-consistent manner and obeying the constraints mandated by thermodynamics. It can calculate the lattice, charge, and thermoelectric transport coefficients for the temperature gradient and electric fields, and the effect of the mutual electron–phonon drag on these transport properties. The code fully exploits the symmetries of the crystal and the transport-active window to allow the sampling of extremely fine electron and phonon wave vector meshes required for accurately capturing the drag phenomena. The coarray feature of modern Fortran, which offers native and convenient support for parallelization, is utilized. The code is compact, readable, well-documented, and extensible by design. © 2022, The Author(s).


  • Basic aspects of the charge density wave instability of transition metal trichalcogenides NbSe3and monoclinic-TaS3

    Guster B., Pruneda M., Ordejón P., Canadell E., Pouget J.-P. Journal of Physics Condensed Matter; 33 (48, 485401) 2021. 10.1088/1361-648X/ac238a. IF: 2.333

    NbSe3 and monoclinic-TaS3 (m-TaS3) are quasi-1D metals containing three different types of chains and undergoing two different charge density wave Peierls transitions at TP1 and TP2 associated with type III and type I chains, respectively. The nature of these transitions is discussed on the basis of first-principles DFT calculation of their Fermi surface (FS) and electron-hole response function. Because of the stronger inter-chain interactions, the FS and electron-hole response function are considerably more complex for NbSe3 than m-TaS3; however a common scenario can be put forward to rationalize the results. The intra-chain inter-band nesting processes dominate the strongest response for both type I and type III chains of the two compounds. Two well-defined maxima of the electron-hole response for NbSe3 are found with the (0a∗, 0c∗) and (1/2a∗, 1/2c∗) transverse components at TP1 and TP2, respectively, whereas the second maximum is not observed for m-TaS3 at TP2. Analysis of the different inter-chain coupling mechanisms leads to the conclusion that FS nesting effects are only relevant to set the transverse a∗ components in NbSe3. The strongest inter-chain Coulomb coupling mechanism must be taken into account for the transverse coupling along c∗ in NbSe3 and along both a∗ and c∗ for m-TaS3. Phonon spectrum calculations reveal the formation of a giant 2kF Kohn anomaly for m-TaS3. All these results support a weak coupling scenario for the Peierls transition of transition metal trichalcogenides. © 2021 IOP Publishing Ltd.

  • Localized electronic vacancy level and its effect on the properties of doped manganites

    Juan D., Pruneda M., Ferrari V. Scientific Reports; 11 (1, 6706) 2021. 10.1038/s41598-021-85945-5. IF: 4.380

    Oxygen vacancies are common to most metal oxides and usually play a crucial role in determining the properties of the host material. In this work, we perform ab initio calculations to study the influence of vacancies in doped manganites La (1 - x)Sr xMnO 3, varying both the vacancy concentration and the chemical composition within the ferromagnetic-metallic range (0.2<x<0.5). We find that oxygen vacancies give rise to a localized electronic level and analyse the effects that the possible occupation of this defect state can have on the physical properties of the host. In particular, we observe a substantial reduction of the exchange energy that favors spin-flipped configurations (local antiferromagnetism), which correlate with the weakening of the double-exchange interaction, the deterioration of the metallicity, and the degradation of ferromagnetism in reduced samples. In agreement with previous studies, vacancies give rise to a lattice expansion when the defect level is unoccupied. However, our calculations suggest that under low Sr concentrations the defect level can be populated, which conversely results in a local reduction of the lattice parameter. Although the exact energy position of this defect level is sensitive to the details of the electronic interactions, we argue that it is not far from the Fermi energy for optimally doped manganites (x∼1/3), and thus its occupation could be tuned by controlling the number of available electrons, either with chemical doping or gating. Our results could have important implications for engineering the electronic properties of thin films in oxide compounds. © 2021, The Author(s).

  • Metallic Diluted Dimerization in VO2 Tweeds

    Sandiumenge F., Rodríguez L., Pruneda M., Magén C., Santiso J., Catalan G. Advanced Materials; 33 (9, 2004374) 2021. 10.1002/adma.202004374. IF: 30.849

    The observation of electronic phase separation textures in vanadium dioxide, a prototypical electron-correlated oxide, has recently added new perspectives on the long standing debate about its metal–insulator transition and its applications. Yet, the lack of atomically resolved information on phases accompanying such complex patterns still hinders a comprehensive understanding of the transition and its implementation in practical devices. In this work, atomic resolution imaging and spectroscopy unveils the existence of ferroelastic tweed structures on ≈5 nm length scales, well below the resolution limit of currently used spectroscopic imaging techniques. Moreover, density functional theory calculations show that this pretransitional fine-scale tweed, which on average looks and behaves like the standard metallic rutile phase, is in fact weaved by semi-dimerized chains of vanadium in a new monoclinic phase that represents a structural bridge to the monoclinic insulating ground state. These observations provide a multiscale perspective for the interpretation of existing data, whereby phase coexistence and structural intermixing can occur all the way down to the atomic scale. © 2021 Wiley-VCH GmbH

  • Structural and magnetic phase diagram of epitaxial La0.7Sr0.3MnO3from first principles

    Pilo J., Pruneda M., Bristowe N.C. Electronic Structure; 3 (2, 024001) 2021. 10.1088/2516-1075/abe6af. IF: 0.000

    ABO3perovskites host a huge range of symmetry lowering structural distortions, each of which can tune, or even switch on or off, different functional properties due to the strong coupling between the lattice, spin and charge degrees of freedom in these materials. The sheer number of different meta-stable structures present in perovskites creates a challenge for materials design via theory and simulation. Here, we tackle this issue using a first principles structure searching method on a prototypical half-metallic perovskite, La0.7Sr0.3MnO3, to predict how epitaxial strain can engineer structural and magnetic properties.We reveal a rich structural phase diagram through strain engineering in which the octahedral tilt pattern, and hence the crystal symmetry, is altered from the bulk.We show how the low-symmetry of the various phases in turn induces new structural modes, an increase in the magnetic anisotropy energy, and weak antiferromagnetic spin-canting. © 2021 The Author(s).

  • Validity of the on-site spin-orbit coupling approximation

    Cuadrado R., Robles R., García A., Pruneda M., Ordejón P., Ferrer J., Cerdá J.I. Physical Review B; 104 (19, 195104) 2021. 10.1103/PhysRevB.104.195104. IF: 4.036

    Spin-orbit coupling (SOC) is generally understood as a highly localized interaction within each atom, whereby core electrons holding large J splittings transfer the SOC to the valence electrons of the same atom, while their direct impact on neighbor valence orbitals is usually small. Seivane and Ferrer [Phys. Rev. Lett. 99, 183401 (2007)PRLTAO0031-900710.1103/PhysRevLett.99.183401] proposed an approach within a tight-binding type ab initio framework assuming that the transfer of SOC from core to valence orbitals only takes place when both are on the same atom, leading to the so-called on-site approximation, which then has been successfully applied to a variety of systems. In this work we thoroughly test its general validity by confronting SOC related properties such as spin splittings, spin textures, or magnetic anisotropies calculated under the on-site approximation versus the more general approach where all the contributions to the SOC, including three-center integrals, are explicitly included. After considering a variety of systems with different dimensionalities, all presenting a strong SOC, we conclude that although the on-site approximation often provides accurate results, it breaks down in some systems where 5d electrons are close to the Fermi level due to their strong SOC and moderately large spatial extension. Furthermore, there are a few examples where subtle inaccuracies lead to qualitatively wrong conclusions, the most clear case being the doping of the topological surface state in Bi2Se3(0001). Finally, magnetic anisotropy energies calculated under this approximation tend to be underestimated. © 2021 American Physical Society.


  • Anion ordering transition and Fermi surface electron-hole instabilities in the (TMTSF)2ClO4and (TMTSF)2NO3Bechgaard salts analyzed through the first-principles Lindhard response function

    Guster B., Pruneda M., Ordejón P., Canadell E., Pouget J.-P. Journal of Physics Condensed Matter; 33 (8, 085705) 2020. 10.1088/1361-648X/abc406. IF: 2.705

    The first-principles electron-hole Lindhard response function has been calculated and analyzed in detail for two (TMTSF)2 X (X = ClO4 and NO3) Bechgaard salts undergoing different anion-ordering (AO) transitions. The calculation was carried out using the real triclinic low-temperature structures. The evolution of the electron-hole response with temperature for both relaxed and quenched salts is discussed. It is shown that the 2k F response of the quenched samples of both salts display a low temperature curved and tilted triangular continuum of maxima. This is not the case for the relaxed samples. (TMTSF)2ClO4 in the AO state exhibits a more quasi-1D response than in the non AO state and relaxed (TMTSF)2NO3 shows a sharp maximum. The curved triangular plateau of the quenched samples results from multiple nesting of the warped quasi-1D Fermi surface which implies the existence of a large q range of electron-hole fluctuations. This broad maxima region is around 1% of the Brillouin zone area for the X = ClO4 salt (and X = PF6) but only 0.1% for the X = NO3 salt. It is suggested that the strong reduction of associated SDW fluctuations could explain the non detection of the SDW-mediated superconductivity in (TMTSF)2NO3. The calculated maxima of the Lindhard response nicely account for the modulation wave vector experimentally determined by NMR in the SDW ground state of the two salts. The critical AO wave vector for both salts is located in regions where the Lindhard response is a minimum so that they are unrelated to any electron-hole instability. The present first-principles calculation reveals 3D effects in the Lindhard response of the two salts at low temperature which are considerably more difficult to model in analytical approaches. © 2020 IOP Publishing Ltd.

  • Effect of Cr on the hydrogen storage and electronic properties of BCC alloys: Experimental and first-principles study

    Balcerzak M., Wagstaffe M., Robles R., Pruneda M., Noei H. International Journal of Hydrogen Energy; 45 (53): 28996 - 29008. 2020. 10.1016/j.ijhydene.2020.07.186. IF: 4.939

    Inventing an effective method to store large amounts of hydrogen at room temperature is one of the key challenges in developing a hydrogen-based economy. Metal hydrides have attracted attention owing to their promising hydrogen storage capabilities. We have systematically studied the structural and electronic properties of mechanically synthesized Ti0.5V1.5-xCrx (0 ≤ x ≤ 0.3) alloys and investigated the influence of the addition of Cr atoms on the hydrogen storage properties of vanadium-rich body-centered-cubic (V-BCC) alloys. X-ray diffraction (XRD) results indicate that all alloys are composed of BCC main phase, with the lattice parameters exhibiting no change following chemical modification. The kinetic measurements have revealed that Cr-containing alloys exhibit improved hydrogen uptake. X-ray photoelectron spectroscopy (XPS) measurements have shown that the addition of Cr has a significant effect on the anti-oxidation properties of V-BCC alloys, increasing their chemical activity and thus enhancing the hydrogen storage properties. Moreover, XPS results elucidate the role of activation of the studied materials. Additionally, the electrochemical properties of the negative electrodes (as part of Ni-MHx secondary batteries) made of Ti0.5V1.4-xNi0.1Crx (0 ≤ x ≤ 0.3) system have been studied by cyclic charge-discharge and demonstrate that doping of the V-BCC alloys with Cr can significantly improve the cycle-life stability of anode that exhibits similar discharge performance up to 50 cycles. First principles simulations are used to analyse the changes in the electronic density of states close to the Fermi level, as a function of Cr concentration, as well as binding energies and structural changes upon hydrogen absorption. Furthermore, ab initio studies confirmed that H absorption is favoured with increasing Cr-content. Our study highlights the importance of the addition of Cr to V-BCC alloys on both solid-gas and electrochemical hydrogenation reactions. © 2020 Hydrogen Energy Publications LLC

  • Fermi surface electron-hole instability of the (TMTSF)2PF6 Bechgaard salt revealed by the first-principles Lindhard response function

    Guster B., Pruneda M., Ordejón P., Canadell E., Pouget J.-P. Journal of Physics Condensed Matter; 32 (34, 345701) 2020. 10.1088/1361-648X/ab8522. IF: 2.707

    We report the first-principles DFT calculation of the electron-hole Lindhard response function of the (TMTSF)2PF6 Bechgaard salt using the real triclinic low-temperature structure. The Lindhard response is found to change considerably with temperature. Near the 2k F spin density wave (SDW) instability it has the shape of a broad triangular plateau as a result of the multiple nesting associated with the warped quasi-one-dimensional Fermi surface. The evolution of the 2k F broad maximum as well as the effect of pressure and deuteration is calculated and analyzed. The thermal dependence of the electron-hole coherence length deduced from these calculations compares very well with the experimental thermal evolution of the 2k F bond order wave correlation length. The existence of a triangular plateau of maxima in the low-temperature electron-hole Lindhard response of (TMTSF)2PF6 should favor a substantial mixing of q-dependent fluctuations which can have important consequences in understanding the phase diagram of the 2k F SDW ground state, the mechanism of superconductivity and the magneto-transport of this paradigmatic quasi-one-dimensional material. The first-principles DFT Lindhard response provides a very accurate and unbiased approach to the low-temperature instabilities of (TMTSF)2PF6 which can take into account in a simple way 3D effects and subtle structural variations, thus providing a very valuable tool in understanding the remarkable physics of molecular conductors. © 2020 IOP Publishing Ltd.

  • Siesta: Recent developments and applications

    García A., Papior N., Akhtar A., Artacho E., Blum V., Bosoni E., Brandimarte P., Brandbyge M., Cerdá J.I., Corsetti F., Cuadrado R., Dikan V., Ferrer J., Gale J., García-Fernández P., García-Suárez V.M., García S., Huhs G., Illera S., Korytár R., Koval P., Lebedeva I., Lin L., López-Tarifa P., Mayo S.G., Mohr S., Ordejón P., Postnikov A., Pouillon Y., Pruneda M., Robles R., Sánchez-Portal D., Soler J.M., Ullah R., Yu V.W.-Z., Junquera J. The Journal of chemical physics; 152 (20): 204108. 2020. 10.1063/5.0005077. IF: 2.991

    A review of the present status, recent enhancements, and applicability of the Siesta program is presented. Since its debut in the mid-1990s, Siesta's flexibility, efficiency, and free distribution have given advanced materials simulation capabilities to many groups worldwide. The core methodological scheme of Siesta combines finite-support pseudo-atomic orbitals as basis sets, norm-conserving pseudopotentials, and a real-space grid for the representation of charge density and potentials and the computation of their associated matrix elements. Here, we describe the more recent implementations on top of that core scheme, which include full spin-orbit interaction, non-repeated and multiple-contact ballistic electron transport, density functional theory (DFT)+U and hybrid functionals, time-dependent DFT, novel reduced-scaling solvers, density-functional perturbation theory, efficient van der Waals non-local density functionals, and enhanced molecular-dynamics options. In addition, a substantial effort has been made in enhancing interoperability and interfacing with other codes and utilities, such as wannier90 and the second-principles modeling it can be used for, an AiiDA plugin for workflow automatization, interface to Lua for steering Siesta runs, and various post-processing utilities. Siesta has also been engaged in the Electronic Structure Library effort from its inception, which has allowed the sharing of various low-level libraries, as well as data standards and support for them, particularly the PSeudopotential Markup Language definition and library for transferable pseudopotentials, and the interface to the ELectronic Structure Infrastructure library of solvers. Code sharing is made easier by the new open-source licensing model of the program. This review also presents examples of application of the capabilities of the code, as well as a view of on-going and future developments.

  • Unfolding method for periodic twisted systems with commensurate Moiré patterns

    Sánchez-Ochoa F., Hidalgo F., Pruneda M., Noguez C. Journal of Physics Condensed Matter; 32 (2, 025501) 2020. 10.1088/1361-648X/ab44f0. IF: 2.707

    We present a general unfolding method for the electronic bands of systems with double-periodicity. Within density functional theory with atomic orbitals as basis-set, our method takes into account two symmetry operations of the primitive cell: a standard expansion and a single rotation, letting to elucidate the physical effects associated to the mutual interactions between systems with more than one periodicity. As a result, our unfolding method allows studying the electronic properties of vertically stacked two-dimensional homo-or heterostructures. We apply our method to study 3 × 3single-layer graphene, √13×√ twisted single-layer graphene, and 2√3×2√3 graphene-√7×√7 tungsten disulfide heterostructure with an interlayer angle of 10.9°. Our unfolding method allows observing typical mini gaps reported in heterostructures, as well as other electronic deviations from pristine structures, impossible to distinguish without an unfolding method. We anticipate that this unfolding method can be useful to compare with experiments to elucidate the electronic properties of two-dimensional homo-or heterostructures, where the interlayer angle can be considered as an additional parameter. © 2019 IOP Publishing Ltd.


  • 2 × 2 charge density wave in single-layer TiTe2

    Guster B., Robles R., Pruneda M., Canadell E., Ordejón P. 2D Materials; 6 (1, 015027) 2019. 10.1088/2053-1583/aaf20b. IF: 7.343

    A density functional theory study concerning the origin of the recently reported 2 × 2 charge density wave (CDW) instability in single-layer TiTe2 is reported. It is shown that, whereas calculations employing the semi-local functional PBE favor the undistorted structure, the hybrid functional HSE06 correctly predicts a 2 × 2 distortion. The study suggests that the magnitude of the semimetallic overlap between the valence band top at - and the conduction band bottom at M is a key factor controlling the tendency towards the distortion. It is also shown that tensile strain stabilizes a 2 × 2 CDW, and we suggest that this fact could be further used to induce the instability in doublelayers of TiTe2, which in the absence of strain remain undistorted in the experiment. The driving force for the CDW instability seems to be the same phonon mediated mechanism acting for singlelayer TiSe2, although in single-layer TiTe2 the driving force is smaller, and the semimetallic character is kept below the transition temperature. © 2018 IOP Publishing Ltd.

  • Coexistence of Elastic Modulations in the Charge Density Wave State of 2 H-NbSe 2

    Guster B., Rubio-Verdú C., Robles R., Zaldívar J., Dreher P., Pruneda M., Silva-Guillén J.Á., Choi D.-J., Pascual J.I., Ugeda M.M., Ordejón P., Canadell E. Nano Letters; 19 (5): 3027 - 3032. 2019. 10.1021/acs.nanolett.9b00268. IF: 12.279

    Bulk and single-layer 2H-NbSe 2 exhibit identical charge density wave order (CDW) with a quasi-commensurate 3 × 3 superlattice periodicity. Here we combine scanning tunnelling microscopy (STM) imaging at T = 1 K of 2H-NbSe 2 with first-principles density functional theory (DFT) calculations to investigate the structural atomic rearrangement of this CDW phase. Our calculations for single-layers reveal that six different atomic structures are compatible with the 3 × 3 CDW distortion, although all of them lie on a very narrow energy range of at most 3 meV per formula unit, suggesting the coexistence of such structures. Our atomically resolved STM images of bulk 2H-NbSe 2 unambiguously confirm this by identifying two of these structures. Remarkably, these structures differ from the X-ray crystal structure reported for the bulk 3 × 3 CDW which in fact is also one of the six DFT structures located for the single-layer. Our calculations also show that due to the minute energy difference between the different phases, the ground state of the 3 × 3 CDW could be extremely sensitive to doping, external strain or internal pressure within the crystal. The presence of multiphase CDW order in 2H-NbSe 2 may provide further understanding of its low temperature state and the competition between different instabilities. © 2019 American Chemical Society.

  • Evidence for the weak coupling scenario of the Peierls transition in the blue bronze

    Guster B., Pruneda M., Ordejón P., Canadell E., Pouget J.-P. Physical Review Materials; 3 (5, 055001) 2019. 10.1103/PhysRevMaterials.3.055001. IF: 2.926

    On the basis of first-principles DFT calculations the wave-vector and temperature dependencies of the Lindhard response function of the blue bronze K0.3MoO3 have been calculated. The kFI+kFII interband component of the response, which is responsible for the Peierls instability, has been quantitatively analyzed. It is found that (i) the electron-hole coherence length of this response determines the length scale of the experimental intrachain CDW correlations, and (ii) the intrachain q⥠dependence of such a response also determines the shape of the Kohn anomaly experimentally measured. These findings provide compelling evidence that the Peierls transition of the blue bronze K0.3MoO3 follows the weak electron-phonon coupling scenario in the adiabatic approximation, something that had not yet been proved on the basis of first-principles calculations for a real material. It is proposed that the CDW interchain coupling occurs through a Coulomb coupling between dipolar CDWs. The nature of the phonon mode leading to the dipolar nature of the CDWs is also discussed, and the relevance of these results to rationalize the CDW instabilities in other oxides and bronzes is pointed out. These findings are also contrasted with recent results for other CDW materials like chalcogenides and tellurides. © 2019 American Physical Society.

  • Guidelines for selecting interlayer spacers in synthetic 2D-based antiferromagnets from first-principles simulations

    Cuadrado R., Pruneda M. Nanomaterials; 9 (12, 1764) 2019. 10.3390/nano9121764. IF: 4.034

    Following the recent synthesis of graphene–based antiferromagnetic ultrathin heterostructures made of Co and Fe, we analyse the effect of the spacer between both ferromagnetic materials. Using density functional calculations, we carried out an exhaustive study of the geometric, electronic and magnetic properties for intercalated single Co MLs on top of Ir(111) coupled to monolayered Fe through n graphene layers (n = 1, 2, 3) or monolayered h-BN. Different local atomic arrangements have been considered to model the Moiré patterns expected in these heterostructures. The magnetic exchange interactions between both ferromagnets (JCo−Fe) are computed from explicit calculations of parallel and anti-parallel Fe/Co inter–layer alignments, and discussed in the context of recent experiments. Our analysis confirms that the robust antiferromagnetic superexchange–coupling between Fe and Co layers is mediated by the graphene spacer through the hybridization of C’s pz orbitals with Fe and Co’s 3d states. The hybridization is substantially suppressed for multilayered graphene spacers, for which the magnetic coupling between ferromagnets is critically reduced, suggesting the need for ultrathin (monolayer) spacers in the design of synthetic graphene-based antiferromagnets. In the case of h–BN, pz orbitals also mediate d(Fe/Co) coupling. However, there is a larger contribution of local ferromagnetic interactions. Magnetic anisotropy energies were also calculated using a fully relativistic description, and show out–of–plane easy axis for all the configurations, with remarkable net values in the range from 1 to 4 meV. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.


  • First principles analysis of the CDW instability of single-layer 1T-TiSe2 and its evolution with charge carrier density

    Guster B., Canadell E., Pruneda M., Ordejón P. 2D Materials; 5 (2, 025024) 2018. 10.1088/2053-1583/aab568. IF: 7.042

    We present a density functional theory study of the electronic structure of single-layer TiSe2, and focus on the charge density wave (CDW) instability present on this 2D material. We explain the periodicity of the CDW from the phonon band structure of the undistorted crystal, which is unstable under one of the phonon modes at the M point. This can be understood in terms of a partial band gap opening at the Fermi level, which we describe on the basis of the symmetry of the involved crystal orbitals, leading to an energy gain upon the displacement of the atoms following the phonon mode in a 2 × 1 structure. Furthermore, the combination of the corresponding phonons for the three inequivalent M points of the Brillouin zone leads to the 2 × 2 distortion characteristic of the CDW state. This leads to a further opening of a full gap, which reduces the energy of the 2 × 2 structure compared to the 2 × 1 one of a single M point phonon, and makes the CDW structure the most stable one. We also analyze the effect of charge injection into the layer on the structural instability. We predict that the 2 × 2 structure only survives for a certain range of doping levels, both for electrons and for holes, as doping reduces the energy gain due to the gap opening. We predict the transition from the commensurate 2 × 2 distortion to an incommensurate one with increasing wavelength upon increasing the doping level, followed by the appearance of the undistorted 1 × 1 structure for larger carrier concentrations. © 2018 IOP Publishing Ltd.

  • Mechanisms behind the enhancement of thermal properties of graphene nanofluids

    Rodríguez-Laguna M.R., Castro-Alvarez A., Sledzinska M., Maire J., Costanzo F., Ensing B., Pruneda M., Ordejón P., Sotomayor Torres C.M., Gómez-Romero P., Chávez-Ángel E. Nanoscale; 10 (32): 15402 - 15409. 2018. 10.1039/c8nr02762e. IF: 7.233

    While the dispersion of nanomaterials is known to be effective in enhancing the thermal conductivity and specific heat capacity of fluids, the mechanisms behind this enhancement remain to be elucidated. Herein, we report on highly stable, surfactant-free graphene nanofluids, based on N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF), with enhanced thermal properties. An increase of up to 48% in thermal conductivity and 18% in specific heat capacity was measured. The blue shift of several Raman bands with increasing graphene concentration in DMF indicates that there is a modification in the vibrational energy of the bonds associated with these modes, affecting all the molecules in the liquid. This result indicates that graphene has the ability to affect solvent molecules at long-range, in terms of vibrational energy. Density functional theory and molecular dynamics simulations were used to gather data on the interaction between graphene and solvent, and to investigate a possible order induced by graphene on the solvent. The simulations showed a parallel orientation of DMF towards graphene, favoring π-π stacking. Furthermore, a local order of DMF molecules around graphene was observed suggesting that both this special kind of interaction and the induced local order may contribute to the enhancement of the fluid's thermal properties. © The Royal Society of Chemistry.


  • Electrical and Thermal Transport in Coplanar Polycrystalline Graphene-hBN Heterostructures

    Barrios-Vargas J.E., Mortazavi B., Cummings A.W., Martinez-Gordillo R., Pruneda M., Colombo L., Rabczuk T., Roche S. Nano Letters; 17 (3): 1660 - 1664. 2017. 10.1021/acs.nanolett.6b04936. IF: 12.712

    We present a theoretical study of electronic and thermal transport in polycrystalline heterostructures combining graphene (G) and hexagonal boron nitride (hBN) grains of varying size and distribution. By increasing the hBN grain density from a few percent to 100%, the system evolves from a good conductor to an insulator, with the mobility dropping by orders of magnitude and the sheet resistance reaching the MΩ regime. The Seebeck coefficient is suppressed above 40% mixing, while the thermal conductivity of polycrystalline hBN is found to be on the order of 30-120 Wm-1 K-1. These results, agreeing with available experimental data, provide guidelines for tuning G-hBN properties in the context of two-dimensional materials engineering. In particular, while we proved that both electrical and thermal properties are largely affected by morphological features (e.g., by the grain size and composition), we find in all cases that nanometer-sized polycrystalline G-hBN heterostructures are not good thermoelectric materials. © 2017 American Chemical Society.

  • Electrochemical behavior of nanostructured La0.8Sr0.2MnO3 as cathodes for solid oxide fuel cells

    Sacanell J., Sánchez J.H., Rubio Lopez A.E., Martinelli H., Siepe J., Leyva A.G., Ferrari V.P., Pruneda M., Juan D., Lamas D.G. ECS Transactions; 78 (1): 667 - 675. 2017. 10.1149/07801.0667ecst. IF: 0.000

    La0.8Sr0.2MnO3 (LSM) is one of the most commonly used cathodes in Solid Oxide Fuel Cells (SOFC). In spite of the fact that nanostructured cathodes are expected to display improved performance, the high operating temperature (∼ 1000°C) of LSM-based SOFCs hinders their stability. In the present work, we have developed nanostructured cathodes prepared from LSM nanotubes of enhanced performance, allowing its use at lower temperatures (∼ 800°C). We observed that our cathodes have qualitative improvements compared with microstructured materials: firstly, the diffusion in the gas phase is optimized to a negligible level and secondly, evidence of ionic conduction is found, which is extremely rare in LSM cathodes. We propose that this important change in the electrochemical properties is due to the nanostructuration of the cathode and deserves further attention, including the exploration of other materials. © The Electrochemical Society.

  • Graphene-based synthetic antiferromagnets and ferrimagnets

    Gargiani P., Cuadrado R., Vasili H.B., Pruneda M., Valvidares M. Nature Communications; 8 (1, 699) 2017. 10.1038/s41467-017-00825-9. IF: 12.124

    Graphene-spaced magnetic systems with antiferromagnetic exchange-coupling offer exciting opportunities for emerging technologies. Unfortunately, the in-plane graphene-mediated exchange-coupling found so far is not appropriate for realistic exploitation, due to being weak, being of complex nature, or requiring low temperatures. Here we establish that ultra-thin Fe/graphene/Co films grown on Ir(111) exhibit robust perpendicular antiferromagnetic exchange-coupling, and gather a collection of magnetic properties well-suited for applications. Remarkably, the observed exchange coupling is thermally stable above room temperature, strong but field controllable, and occurs in perpendicular orientation with opposite remanent layer magnetizations. Atomistic first-principles simulations provide further ground for the feasibility of graphene-spaced antiferromagnetic coupled structures, confirming graphene's direct role in sustaining antiferromagnetic superexchange-coupling between the magnetic films. These results provide a path for the realization of graphene-based perpendicular synthetic antiferromagnetic systems, which seem exciting for fundamental nanoscience or potential use in spintronic devices. © 2017 The Author(s).

  • Oxygen Reduction Mechanisms in Nanostructured La0.8Sr0.2MnO3 Cathodes for Solid Oxide Fuel Cells

    Sacanell J., Hernández Sánchez J., Rubio López A.E., Martinelli H., Siepe J., Leyva A.G., Ferrari V., Juan D., Pruneda M., Mejía Gómez A., Lamas D.G. Journal of Physical Chemistry C; 121 (12): 6533 - 6539. 2017. 10.1021/acs.jpcc.7b00627. IF: 4.536

    In this work we outline the mechanisms contributing to the oxygen reduction reaction in nanostructured cathodes of La0.8Sr0.2MnO3 (LSM) for Solid Oxide Fuel Cells (SOFC). These cathodes, developed from LSM nanostructured tubes, can be used at lower temperatures compared to microstructured ones, and this is a crucial fact to avoid the degradation of the fuel cell components. This reduction of the operating temperatures stems mainly from two factors: (i) the appearance of significant oxide ion diffusion through the cathode material in which the nanostructure plays a key role and (ii) an optimized gas phase diffusion of oxygen through the porous structure of the cathode, which becomes negligible. A detailed analysis of our Electrochemical Impedance Spectroscopy supported by first-principles calculations point toward an improved overall cathodic performance driven by a fast transport of oxide ions through the cathode surface. (Figure Presented). © 2017 American Chemical Society.


  • Noncontact atomic force microscopy and density functional theory studies of the (2×2) reconstructions of the polar AlN(0001) surface

    Chaumeton F., Robles R., Pruneda M., Lorente N., Eydoux B., Bouju X., Gauthier S., Martrou D. Physical Review B; 94 (16, 165305) 2016. 10.1103/PhysRevB.94.165305.

    Combined experimental and theoretical studies permit us to determine new protocols for growing by molecular beam epitaxy the technologically interesting N-rich aluminum nitride (AlN) surfaces. This is achieved by dosing the precursor gases at unusually low rates. With the help of calculated structures by using density functional theory and Boltzmann distribution of the reconstructed cells, we proposed to assign the measured surface obtained with a growth rate of 10 nm/h to a (2×2) reconstructed surface involving one additional N atom per unit cell. These N-rich AlN surfaces could open new routes to dope AlN layers with important implications in high-power and temperature technological applications. © 2016 American Physical Society.


  • Electromechanical response at polar zigzag boundaries in hybrid monolayers

    Martinez-Gordillo R., Pruneda M. Physical Review B - Condensed Matter and Materials Physics; 91 (4, 045411) 2015. 10.1103/PhysRevB.91.045411. IF: 3.736

    First-principles calculations are used to demonstrate electromechanical control of charge and spin at zigzag-edged interfaces between graphene and boron-nitride domains in hybrid monolayers. We show how, through a direct piezoelectric effect, the interfacial bound charges and associated electric fields can be tuned by application of an external mechanical force (stress) on the system. This results in mechanical control of the edge magnetization (piezomagnetic effect), and the possibility to transform a semiconducting heterostructure into a half-metal. The inverse effect (application of an external electric field to induce a mechanical deformation) goes together with a magnetoelectric response, which under ideal conditions we estimate to be comparable to that of prototypical Cr2O3. These effects originate from the magnetic properties of graphene's zigzag edges and the dielectric properties of the boron-nitride domain, and can also be expected in any other coplanar heterostructures with polar discontinuities. © 2015 American Physical Society.

  • Polar discontinuities and 1D interfaces in monolayered materials

    Martinez-Gordillo R., Pruneda M. Progress in Surface Science; 90 (4): 444 - 463. 2015. 10.1016/j.progsurf.2015.08.001. IF: 5.696

    Interfaces are the birthplace of a multitude of fascinating discoveries in fundamental science, and have enabled modern electronic devices, from transistors, to lasers, capacitors or solar cells. These interfaces between bulk materials are always bi-dimensional (2D) 'surfaces'. However the advent of graphene and other 2D crystals opened up a world of possibilities, as in this case the interfaces become one-dimensional (1D) lines. Although the properties of 1D nanoribbons have been extensively discussed in the last few years, 1D interfaces within infinite 2D systems had remained mostly unexplored until very recently. These include grain boundaries in polycrystalline samples, or interfaces in hybrid 2D sheets composed by segregated domains of different materials (as for example graphene/BN hybrids, or chemically different transition metal dichalcogenides). As for their 2D counterparts, some of these 1D interfaces exhibit polar characteristics, and can give rise to fascinating new physical properties. Here, recent experimental discoveries and theoretical predictions on the polar discontinuities that arise at these 1D interfaces will be reviewed, and the perspectives of this new research topic, discussed. © 2015 Elsevier Ltd. All rights reserved.


  • Piezoelectric 2D materials for bistable NEMS energy harvesters

    López-Suárez M., Pruneda M., Rurali R., Abadal G. International Review of the Red Cross; 1701 (1) 2014. 10.1557/opl.2014.484.

    The dynamics of one atom thick h-BN suspended nanoribbons have been obtained by first performing ab-initio calculations of the deformation potential energy and then solving numerically a Langevine type equation to explore their use as energy harvesting devices. Similarly to our previous proposal for a graphene-based harvester1, an applied compressive strain is used to drive the clamped-clamped nanoribbon structure into a bistable regime, where quasi-harmonic vibrations are combined with low frequency swings between the minima of a double-well potential. h-BN, graphene and MoS2 similar structures have been compared in terms of the static response to a compressive strain and of the dynamic evolution induced by an external noisy vibration. Due to its intrinsic piezoelectric response, the mechanical harvester naturally provides an electrical power that is readily available or can be stored by simply contacting the monolayer at its ends. Engineering the induced non-linearity, the proposed device is predicted to harvest an electrical root mean square (rms) power of more than 180 fW when it is excited by a noisy external force characterized by a white Gaussian frequency distribution with an intensity in the order of Frms=5pN. © 2014 Materials Research Society.

  • Piezoelectric monolayers as nonlinear energy harvesters

    López-Suárez, M.; Pruneda, M.; Abadal, G.; Rurali, R. Nanotechnology; 2014. 10.1088/0957-4484/25/17/175401. IF: 3.672

  • Theoretical study on the influence of the Mg2+ and Al3+ octahedral cations on the vibrational spectra of the hydroxy groups of dioctahedral 2:1 phyllosilicate models

    Hernández-Haro, N.; Ortega-Castro, J.,; Pruneda, M.,; Sainz-Díaz, C.I.,; Hernández-Laguna, A. Journal of Molecular Modeling; 20 (9): 2402. 2014. 10.1007/s00894-014-2402-6. IF: 1.867

  • Transport fingerprints at graphene superlattice Dirac points induced by a boron nitride substrate

    Martinez-Gordillo, R.; Roche, S.; Ortmann, F.; Pruneda, M. Physical Review B - Condensed Matter and Materials Physics; 2014. 10.1103/PhysRevB.89.161401. IF: 3.664


  • Electrochemical ferroelectric switching: Origin of polarization reversal in ultrathin films

    Bristowe, N.C.; Stengel, M.; Littlewood, P.B.; Pruneda, J.M.; Artacho, E. Physical Review B - Condensed Matter and Materials Physics; 85 2012. 10.1103/PhysRevB.85.024106.

  • Native defects in hybrid C/BN nanostructures by density functional theory calculations

    Pruneda, J.M. Physical Review B - Condensed Matter and Materials Physics; 85 2012. 10.1103/PhysRevB.85.045422.


  • Band selection and disentanglement using maximally localized Wannier functions: The cases of Co impurities in bulk copper and the Cu(111) surface

    Korytár R., Pruneda M., Junquera J., Ordejón P., Lorente N. Journal of Physics Condensed Matter; 22 (38, 385601) 2010. 10.1088/0953-8984/22/38/385601.

    We have adapted the maximally localized Wannier function approach of Souza et al (2002 Phys. Rev. B 65 035109) to the density functional theory based Siesta code (Soler et al 2002 J. Phys.: Condens. Mater. 14 2745) and applied it to the study of Co substitutional impurities in bulk copper as well as to the Cu(111) surface. In the Co impurity case, we have reduced the problem to the Co d-electrons and the Cu sp-band, permitting us to obtain an Anderson-like Hamiltonian from well defined density functional parameters in a fully orthonormal basis set. In order to test the quality of the Wannier approach to surfaces, we have studied the electronic structure of the Cu(111) surface by again transforming the density functional problem into the Wannier representation. An excellent description of the Shockley surface state is attained, permitting us to be confident in the application of this method to future studies of magnetic adsorbates in the presence of an extended surface state. © 2010 IOP Publishing Ltd.

  • Origin of half-semimetallicity induced at interfaces of C-BN heterostructures

    Pruneda, J.M. Physical Review B - Condensed Matter and Materials Physics; 81 2010. 10.1103/PhysRevB.81.161409.

  • Real-time TD-DFT simulations in dye sensitized solar cells: The electronic absorption spectrum of alizarin supported on TiO2 nanoclusters

    Sánchez-De-Armas R., Oviedo López J., San-Miguel M.A., Sanz J.F., Ordejón P., Pruneda M. Journal of Chemical Theory and Computation; 6 (9): 2856 - 2865. 2010. 10.1021/ct100289t.

    The structural and electronic properties of the alizarin dye supported on TiO2 nanoclusters have been examined by means of time-dependent density-functional (TD-DFT) calculations performed in the time-domain framework. The calculated electronic absorption spectrum of free alizarin shows a first band centered at 2.67 eV that upon adsorption features a red shift by 0.31 eV, in agreement with both experimental and previous theoretical work. This red shift arises from a relative stabilization of the dye LUMO when adsorbed. To analyze the dependence of the electronic properties of the dye-support couple on the size of metal-oxide nanoparticles, different models of (TiO 2)n nanoclusters have been used (with n = 1, 2, 3, 6, 9, 15, and 38). As a conclusion, the minimal model is good enough to theoretically reproduce the main feature in the spectrum (i.e., the energy shift of the main band upon binding to TiO2). However, it fails in creating intermediate states which could play a significant role under real experimental conditions (dynamics of the electronic transfer). Indeed, as the size of the nanocluster grows, the dye LUMO moves from the edge to well inside the conduction band (Ti 3d band). On the other hand, to assess the consistency of the time-domain approach in the case of such systems, conventional (frequency-domain) TD-DFT calculations have been carried out. It is found that, as far as the functional and basis set are equivalent, both approaches lead to similar results. While for small systems the standard TD-DFT is better suited, for medium to large sized systems, the real-time TD-DFT becomes competitive and more efficient. © 2010 American Chemical Society.


  • He-LiF surface interaction potential from fast atom diffraction

    Schüller, A.; Winter, H.; Gravielle, M.S.; Pruneda, J.M.; Miraglia, J.E. PHYSICAL REVIEW A; 80 2009. 10.1103/PhysRevA.80.062903.

  • Nonadiabatic wavepacket dynamics: K-space formulation

    Pruneda, J.M.; Souza, I. Physical Review B - Condensed Matter and Materials Physics; 79 2009. 10.1103/PhysRevB.79.045127.


  • The SIESTA method; Developments and applicability

    Artacho E., Anglada E., Diéguez O., Gale J.D., García A., Junquera J., Martin R.M., Ordejón P., Pruneda J.M., Sánchez-Portal D., Soler J.M. Journal of Physics Condensed Matter; 20 (6, 064208) 2008. 10.1088/0953-8984/20/6/064208.

    Recent developments in and around the SIESTA method of first-principles simulation of condensed matter are described and reviewed, with emphasis on (i) the applicability of the method for large and varied systems, (ii) efficient basis sets for the standards of accuracy of density-functional methods, (iii) new implementations, and (iv) extensions beyond ground-state calculations. © 2008 IOP Publishing Ltd.


  • First-principles study of structural, elastic, and bonding properties of pyrochlores

    J.M. Pruneda; Emilio Artacho Physical Review B - Condensed Matter and Materials Physics; 2005. .


  • Intrinsic point defects and volume swelling in ZrSiO4 under irradiation

    J. M. Pruneda; T. D. Archer; Emilio Artacho Physical Review B - Condensed Matter and Materials Physics; 2004. .

  • Short-range repulsive interatomic interactions in energetic processes in solids

    J. M. Pruneda; Emilio Artacho Physical Review B - Condensed Matter and Materials Physics; 2004. .