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Subject: search.filters.subject.530Institute: search.filters.UBSInstitut.Institut für MaterialwissenschaftStart date: 2020Author: search.filters.author.Srinivasan, Prashanth

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Now showing 1 - 6 of 6
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    High-accuracy thermodynamic properties to the melting point from ab initio calculations aided by machine-learning potentials
    (2023) Jung, Jong Hyun; Srinivasan, Prashanth; Forslund, Axel; Grabowski, Blazej
    Accurate prediction of thermodynamic properties requires an extremely accurate representation of the free-energy surface. Requirements are twofold - first, the inclusion of the relevant finite-temperature mechanisms, and second, a dense volume–temperature grid on which the calculations are performed. A systematic workflow for such calculations requires computational efficiency and reliability, and has not been available within an ab initio framework so far. Here, we elucidate such a framework involving direct upsampling, thermodynamic integration and machine-learning potentials, allowing us to incorporate, in particular, the full effect of anharmonic vibrations. The improved methodology has a five-times speed-up compared to state-of-the-art methods. We calculate equilibrium thermodynamic properties up to the melting point for bcc Nb, magnetic fcc Ni, fcc Al, and hcp Mg, and find remarkable agreement with experimental data. A strong impact of anharmonicity is observed specifically for Nb. The introduced procedure paves the way for the development of ab initio thermodynamic databases.
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    Li5Sn, the most lithium-rich binary stannide : a combined experimental and computational study
    (2022) Stelzer, Robert U.; Ikeda, Yuji; Srinivasan, Prashanth; Lehmann, Tanja S.; Grabowski, Blazej; Niewa, Rainer
    From reaction of excess lithium with tin, we isolate well-crystallized Li5Sn and solve the crystal structure from single-crystal X-ray diffraction data. The orthorhombic structure (space group Cmcm) features the same coordination polyhedra around tin and lithium as previously predicted by electronic structure calculations for this composition, however differently arranged. An extensive ab initio analysis, including thermodynamic integration using Langevin dynamics in combination with a machine-learning potential (moment tensor potential), is conducted to understand the thermodynamic stability of this Cmcm Li5Sn structure observed in our experiments. Among the 108 Li5Sn structures systematically derived using the structure enumeration algorithm, including the experimental Cmcm structure and those obtained in previous ab initio studies, another new structure with the space group Immm is found to be energetically most stable at 0 K. This computationally discovered Immm structure is also found to be thermodynamically more stable than the Cmcm structure at finite temperatures, indicating that the Cmcm Li5Sn structure observed in our experiments is favored likely due to kinetic reasons rather than thermodynamics.
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    Anharmonicity in bcc refractory elements : a detailed ab initio analysis
    (2023) Srinivasan, Prashanth; Shapeev, Alexander; Neugebauer, Jörg; Körmann, Fritz; Grabowski, Blazej
    Explicit anharmonicity, defined as the vibrational contribution beyond the quasiharmonic approximation, is qualitatively different between the group V and group VI bcc refractory elements. Group V elements show a small and mostly negative anharmonic entropy, whereas group VI elements have a large positive anharmonic entropy, strongly increasing with temperature. Here, we explain this difference utilizing highly accurate anharmonic free energies and entropies from ab initio calculations for Nb and Ta (group V), and Mo and W (group VI). The numerically calculated entropies are in agreement with prior experimental data. The difference in behavior between the two sets of elements arises not from their high-temperature behavior but rather from the 0K　quasiharmonic reference state. We understand this by analyzing the 0K and the high-temperature phonon density of states and the electronic density of states. The qualitative difference disappears when the anharmonicity is instead referenced with a high-temperature effective harmonic potential. However, even for an optimized effective harmonic reference, the remaining effective anharmonicity is significant. The reason is that the anharmonicity in the bcc systems - carried by asymmetric distributions in the nearest neighbors - can never be accounted for by a harmonically restricted potential.
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    Thermodynamics up to the melting point in a TaVCrW high entropy alloy : systematic ab initio study aided by machine learning potentials
    (2022) Zhou, Ying; Srinivasan, Prashanth; Körmann, Fritz; Grabowski, Blazej; Smith, Roger; Goddard, Pooja; Duff, Andrew Ian
    Multi-principal-component alloys have attracted great interest as a novel paradigm in alloy design, with often unique properties and a vast compositional space auspicious for materials discovery. High entropy alloys (HEAs) belong to this class and are being investigated for prospective nuclear applications with reported superior mechanical properties including high-temperature strength and stability compared to conventional alloys. Computational materials design has the potential to play a key role in screening such alloys, yet for high-temperature properties, challenges remain in finding an appropriate balance between accuracy and computational cost. Here we develop an approach based on density-functional theory (DFT) and thermodynamic integration aided by machine learning based interatomic potential models to address this challenge. We systematically evaluate and compare the efficiency of computing the full free energy surface and thermodynamic properties up to the melting point at different stages of the thermodynamic integration scheme. Our new approach provides a ×4 speed-up with respect to comparable free energy approaches at the level of DFT, with errors on high-temperature free energy predictions less than 1 meV/atom. Calculations are performed on an equiatomic HEA, TaVCrW - a low-activation composition and therefore of potential interest for next generation fission and fusion reactors.
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    Performance of two complementary machine-learned potentials in modelling chemically complex systems
    (2023) Gubaev, Konstantin; Zaverkin, Viktor; Srinivasan, Prashanth; Duff, Andrew Ian; Kästner, Johannes; Grabowski, Blazej
    Chemically complex multicomponent alloys possess exceptional properties derived from an inexhaustible compositional space. The complexity however makes interatomic potential development challenging. We explore two complementary machine-learned potentials - the moment tensor potential (MTP) and the Gaussian moment neural network (GM-NN) - in simultaneously describing configurational and vibrational degrees of freedom in the Ta-V-Cr-W alloy family. Both models are equally accurate with excellent performance evaluated against density-functional-theory. They achieve root-mean-square-errors (RMSEs) in energies of less than a few meV/atom across 0 K ordered and high-temperature disordered configurations included in the training. Even for compositions not in training, relative energy RMSEs at high temperatures are within a few meV/atom. High-temperature molecular dynamics forces have similarly small RMSEs of about 0.15 eV/Å for the disordered quaternary included in, and ternaries not part of training. MTPs achieve faster convergence with training size; GM-NNs are faster in execution. Active learning is partially beneficial and should be complemented with conventional human-based training set generation.
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    Thermodynamic properties on the homologous temperature scale from direct upsampling : understanding electron-vibration coupling and thermal vacancies in bcc refractory metals
    (2023) Forslund, Axel; Jung, Jong Hyun; Srinivasan, Prashanth; Grabowski, Blazej
    We have calculated thermodynamic properties of four bcc refractory elements - V, Ta, Mo, and W - up to the melting point with full density-functional-theory accuracy, using the recently developed direct-upsampling method [J. H. Jung et al., npj Comput. Mater. 9, 3 (2023)]. The direct-upsampling methodology takes full account of explicit anharmonic vibrations and electron-vibration coupling very efficiently using machine-learning potentials. We have thus been able to compute highly converged free-energy surfaces for the PBE exchange-correlation functional, from which accurate temperature dependencies of various thermodynamic properties such as the heat capacity, thermal expansion coefficient, and bulk modulus are accessible. For all four elements, the electronic contribution is large, including a strong coupling with the thermal vibrations. The atomic forces in W are even affected by the temperature-consistent Fermi broadening, which alters the free energy by around 3 meV/atom at the melting point. Trends within group V and group VI refractory elements are observed and explained by qualitative differences in the electronic density of states. We also provide an estimate of the Gibbs energies of vacancy formation and the vacancy contribution to the thermodynamics. Lastly and most importantly, our results are analyzed in terms of the homologous temperature scale relative to theoretically predicted melting points (for the PBE functional). The homologous temperature dependencies show a remarkable agreement with experiments and reveal the predictive power of self-consistently determined ab initio thermodynamic properties.