Efficient and accurate determination of lattice-vacancy diffusion coefficients via non equilibrium ab initio molecular dynamics

We revisit the color-diffusion algorithm [P. C. Aeberhard et al., Phys. Rev. Lett. 108, 095901 (2012)] in nonequilibrium ab initio molecular dynamics (NE-AIMD), and propose a simple efficient approach for the estimation of monovacancy jump rates in crystalline solids at temperatures well below melting. Color-diffusion applied to monovacancy migration entails that one lattice atom (colored-atom) is accelerated toward the neighboring defect-site by an external constant force F. Considering bcc molybdenum between 1000 and 2800 K as a model system, NE-AIMD results show that the colored-atom jump rate k_{NE} increases exponentially with the force intensity F, up to F values far beyond the linear-fitting regime employed previously. Using a simple model, we derive an analytical expression which reproduces the observed k_{NE}(F) dependence on F. Equilibrium rates extrapolated by NE-AIMD results are in excellent agreement with those of unconstrained dynamics. The gain in computational efficiency achieved with our approach increases rapidly with decreasing temperatures, and reaches a factor of four orders of magnitude at the lowest temperature considered in the present study

Temperature dependent effective potential method for accurate free energy calculations of solids

We have developed a thorough and accurate method of determining anharmonic free energies, the temperature dependent effective potential technique (TDEP). It is based on \emph{ab initio} molecular dynamics followed by a mapping onto a model Hamiltonian that describes the lattice dynamics. The formalism and the numerical aspects of the technique are described in details. A number of practical examples are given, and results are presented, which confirm the usefulness of TDEP within \emph{ab initio} and classical molecular dynamics frameworks. In particular, we examine from first-principles the behavior of force constants upon the dynamical stabilization of body centered phase of Zr, and show that they become more localized. We also calculate phase diagram for $^4$He modeled with the Aziz \emph{et al.} potential and obtain results which are in favorable agreement both with respect to experiment and established techniques

Lattice Thermal Conductivity of Polyethylene Molecular Crystals from First-Principles Including Nuclear Quantum Effects

Molecular crystals such as polyethylene are of intense interest as flexible thermal conductors, yet their intrinsic upper limits of thermal conductivity remain unknown. Here, we report a study of the vibrational properties and lattice thermal conductivity of a polyethylene molecular crystal using an ab initio approach that rigorously incorporates nuclear quantum motion and finite temperature effects. We obtain a thermal conductivity along the chain direction of around 160  W m^(-1) K^(-1) at room temperature, providing a firm upper bound for the thermal conductivity of this molecular crystal. Furthermore, we show that the inclusion of quantum nuclear effects significantly impacts the thermal conductivity by altering the phase space for three-phonon scattering. Our computational approach paves the way for ab initio studies and computational material discovery of molecular solids free of any adjustable parameters

Electron-Phonon Scattering in the Presence of Soft Modes and Electron Mobility in SrTiO3_{3} Perovskite from First Principles

Structural phase transitions and soft phonon modes pose a longstanding challenge to computing electron-phonon (e-ph) interactions in strongly anharmonic crystals. Here we develop a first-principles approach to compute e-ph scattering and charge transport in materials with anharmonic lattice dynamics. Our approach employs renormalized phonons to compute the temperature-dependent e-ph coupling for all phonon modes, including the soft modes associated with ferroelectricity and phase transitions. We show that the electron mobility in cubic SrTiO$_{3}$ is controlled by scattering with longitudinal optical phonons at room temperature and with ferroelectric soft phonons below 200~K. Our calculations can accurately predict the temperature dependence of the electron mobility in SrTiO$_{3}$ between 150$-$300~K, and reveal the microscopic origin of its roughly $T^{-3}$ trend. Our approach enables first-principles calculations of e-ph interactions and charge transport in broad classes of crystals with phase transitions and strongly anharmonic phonons.Comment: 5 pages, 3 figures. Updated to published versio

Anharmonicity changes the solid solubility of an alloy at high temperatures

We have developed a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti$_{1-x}$Al$_x$N alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy, corresponding to the true equilibrium state of the system. We demonstrate that the anharmonic contribution and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti$_{1-x}$Al$_x$N alloy, lowering the maximum temperature for the miscibility gap from 6560 K to 2860 K. Our local chemical composition measurements on thermally aged Ti$_{0.5}$Al$_{0.5}$N alloys agree with the calculated phase diagram.Comment: 4 pages, 5 figures, supplementary materia

Thermal conductivity in PbTe from first principles

We investigate the harmonic and anharmonic contributions to the phonon spectrum of lead telluride and perform a complete characterization of how thermal properties of PbTe evolve as temperature increases. We analyze the thermal resistivity's variation with temperature and clarify misconceptions about existing experimental literature. The resistivity initially increases sublinearly because of phase space effects and ultra strong anharmonic renormalizations of specific bands. This effect is the strongest factor in the favorable thermoelectric properties of PbTe, and it explains its limitations at higher T . This quantitative prediction opens the prospect of phonon phase space engineering to tailor the lifetimes of crucial heat carrying phonons by considering different structure or nanostructure geometries. We analyze the available scattering volume between TO and LA phonons as a function of temperature and correlate its changes to features in the thermal conductivity