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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.
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A density-functional-theory based approach to efficiently compute numerically exact vibrational free energies - including anharmonicity - for chemically complex multicomponent alloys is developed. It is based on a combination of thermodynamic integration and a machine-learning potential. We demonstrate the performance of the approach by computing the anharmonic free energy of the prototypical five-component VNbMoTaW refractory high entropy alloy.
We examine anharmonic contributions to the optical phonon modes in bulk $T_d$-MoTe$_2$ through temperature-dependent Raman spectroscopy. At temperatures ranging from 100 K to 200 K, we find that all modes redshift linearly with temperature in agreement with the Gr{u}neisen model. However, below 100 K we observe nonlinear temperature-dependent frequency shifts in some modes. We demonstrate that this anharmonic behavior is consistent with the decay of an optical phonon into multiple acoustic phonons. Furthermore, the highest frequency Raman modes show large changes in intensity and linewidth near $Tapprox 250$ K that correlate well with the $T_d to 1T^prime$ structural phase transition. These results suggest that phonon-phonon interactions can dominate anharmonic contributions at low temperatures in bulk $T_d$-MoTe$_2$, an experimental regime that is currently receiving attention in efforts to understand Weyl semimetals.
Recent measurements of an unusual high thermal conductivity of around 1000 W m-1 K-1 at room temperature in cubic boron arsenide (BAs) confirm predictions from theory and suggest potential applications of this semiconductor compound for thermal management applications. Knowledge of the thermal expansion coefficient and Gruneisen parameter of a material contributes both to the fundamental understanding of its lattice anharmonicity and to assessing its utility as a thermal-management material. However, previous theoretical calculations of the thermal expansion coefficient and Gruneisen parameter of BAs yield inconsistent results. Here we report the linear thermal expansion coefficient of BAs obtained from the X-ray diffraction measurements from 300 K to 773 K. The measurement results are in good agreement with our ab initio calculations that account for atomic interactions up to fifth nearest neighbours. With the measured thermal expansion coefficient and specific heat, a Gruneisen parameter of BAs of 0.84 +/- 0.09 is obtained at 300 K, in excellent agreement with the value of 0.82 calculated from first principles and much lower than prior theoretical results. Our results confirm that BAs exhibits a better thermal expansion coefficient match with commonly used semiconductors than other high-thermal conductivity materials such as diamond and cubic boron nitride.
Theoretical calculations of sound-wave velocities of materials at extreme conditions are of great importance to various fields, in particular geophysics. For example, the seismic data on sound-wave propagation through the solid iron-rich Earths inner core have been the main source for elucidating its properties and building models. As the laboratory experiments at very high temperatures and pressures are non-trivial, ab initio predictions are invaluable. The latter, however, tend to disagree with experiment. We notice that many attempts to calculate sound-wave velocities of matter at extreme conditions in the framework of quantum-mechanics based methods have not been taking into account the effect of anharmonic atomic vibrations. We show how anharmonic effects can be incorporated into ab initio calculations and demonstrate that in particular they might be non-negligible for iron in Earths core. Therefore, we open an avenue to reconcile experiment and ab initio theory.
Closed-shell light-emitting diodes (LEDs) suffer from the internal quantum efficiency (IQE) limitation imposed by optically inactive triplet excitons. Here we show an undiscovered emission mechanism of lead-halide-perovskites (LHPs) APbX$_3$ (A=Cs/CN$_2$H$_5$; X=Cl/Br/I) that circumvents the efficiency limit of closed-shell LEDs. Though efficient emission is prohibited by optically inactive $J=0$ in inversion symmetric LHPs, the anharmonicity arising from stereochemistry of Pb and resonant orbital-bonding network along the imaginary A$^+cdots$X$^-$ (T$_{1u}$) transverse optical (TO) modes, breaks the inversion symmetry and introduces disorder and Rashba-Dresselhaus spin-orbit coupling (RD-SOC). This leads to bright co-helical and dark anti-helical excitons. Many-body theory and first-principles calculations affirm that the optically active co-helical exciton is the lowest excited state in organic/inorganic LHPs. Thus, RD-SOC can drive to achieve the ideal 50 $%$ IQE by utilizing anharmonicity, much over the 25 $%$ IQE limitation for closed-shell LEDs.
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