Abstract
Theoretical frameworks used to qualitatively and quantitatively describe nuclear dynamics in solids are often based on the harmonic approximation. However, this approximation is known to become inaccurate or to break down completely in many modern functional materials. Interestingly, there is no reliable measure to quantify anharmonicity so far. Thus, a systematic classification of materials in terms of anharmonicity and a benchmark of methodologies that may be appropriate for different strengths of anharmonicity is currently impossible. In this work, we derive and discuss a statistical measure that reliably classifies compounds across temperature regimes and material classes by their "degree of anharmonicity". This enables us to distinguish "harmonic" materials, for which anharmonic effects constitute a small perturbation on top of the harmonic approximation, from strongly "anharmonic" materials, for which anharmonic effects become significant or even dominant and the treatment of anharmonicity in terms of perturbation theory is more than questionable. We show that the analysis of this measure in real and reciprocal space is able to shed light on the underlying microscopic mechanisms, even at conditions close to, e.g., phase transitions or defect formation. Eventually, we demonstrate that the developed approach is computationally efficient and enables rapid high-throughput searches by scanning over a set of several hundred binary solids. The results show that strong anharmonic effects beyond the perturbative limit are not only active in complex materials or close to phase transitions, but already at moderate temperatures in simple binary compounds.
Highlights
In condensed-matter physics and materials science, the dynamics of nuclei plays a decisive role for many materials properties
The results show that strong anharmonic effects beyond the perturbative limit are active in complex materials or close to phase transitions, but already at moderate temperatures in simple binary compounds
We investigate both compounds at room temperature via ab initio molecular dynamics (aiMD) simulations [27] at the generalized gradient approximation (GGA) level of theory using the PBEsol exchangecorrelation functional [28], light default basis sets [29], and a Langevin thermostat [30] to perform canonical sampling in supercells of 216 atoms (Si) and 160 atoms (KCaF3), respectively
Summary
In condensed-matter physics and materials science, the dynamics of nuclei plays a decisive role for many materials properties. Material properties and phenomena that are described inaccurately or not at all within such a harmonic model are generally referred to as anharmonic effects These effects include (i) the temperature dependence of equilibrium properties like thermal lattice expansion, (ii) thermal shift of vibrational frequencies and linewidth broadening, (iii) phase transitions, and (iv) heat transport. We address this open issue by deriving and validating the required anharmonicity measure As discussed below, it (i) allows for a systematic and quantitative classification of compounds across material space from systems with only mild anharmonic contributions, to strongly anharmonic systems where the phonon picture is invalid, (ii) establishes a link between the actuating microscopic mechanisms and macroscopic properties, and (iii) requires a fraction of the computational cost of either perturbative or aiMD calculations and paves the way for high-throughput anharmonicity classification of materials.
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