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The objective is to develop atomistic potentials systematically and efficiently for a variety of materials science applications. We aim to make these potentials and training datasets freely available to the scientific community., This work is supported by National Science Foundation, Award No. CSSI-2003808

Halide perovskites are strongly influenced by large amplitude anharmonic lattice fluctuations at room temperature. We develop a tight binding model for dynamically disordered MAPbI$_3$ based on density functional theory (DFT) calculations to calculate electronic structure for finite temperature crystal structures at the length scale of thermal disorder and carrier localization. The model predicts individual Hamiltonian matrix elements and band structures with high accuracy, owing to the inclusion of additional matrix elements and descriptors for non-Coulombic interactions. We apply this model to electronic structure at length and time scales inaccessible to first principles methods, finding an increase in band gap, carrier mass, and the sub-picosecond fluctuations in these quantities with increasing temperature as well as the onset of carrier localization in large supercells induced by thermal disorder at 300 K. We identify the length scale $L^*= 5$ nm as the onset of localization in the electronic structure, associated with associated with decreasing band edge fluctuations, increasing carrier mass, and Rashba splitting approaching zero.

The strain-dependent phonon properties and thermal conductivities of a soft system [Lennard-Jones (LJ) argon] and a stiff system (silicon modeled using first-principles calculations) are predicted using lattice dynamics calculations and the Boltzmann transport equation. As is commonly assumed for materials under isotropic strain, the thermal conductivity of LJ argon decreases monotonically as the system moves from compression into tension. The reduction in thermal conductivity is attributed to decreases in both the phonon lifetimes and group velocities. The thermal conductivity of silicon, however, is constant in compression and only begins to decrease once the system is put in tension. The silicon lifetimes show an anomalous behavior, whereby they increase as the system moves from compression into tension, which is explained by examining the potential energy surface felt by an atom. The results emphasize the need to separately consider the harmonic and anharmonic effects of strain on material stiffness, phonon properties, and thermal conductivity.

Using an ab initio atomistic thermodynamics framework, we identify the stable surface structures during the early stages of Cu(100) oxidation at finite temperature and pressure conditions. We predict the clean surface, the 0.25 monolayer oxygen-covered surface, and the missing-row reconstruction as thermodynamically stable structures in range of 100–1000 K and 10−15–105atm, consistent with previous experimental and theoretical results. We also investigate the thermodynamic stabilities of possible precursors to Cu2O formation including missing-row reconstruction structures that include extra on- or subsurface oxygen atoms as well as boundary phases formed from two missing-row nanodomains. While these structures are not predicted to be thermodynamically stable for oxygen chemical potentials below the nucleation limit of Cu2O, they are likely to exist due to kinetic hindrance.

Environmental effects and intrinsic energy-loss processes lead to fluctuations in the operational temperature of solar cells, which can profoundly influence their power conversion efficiency. Here we determine from first-principles the effects of temperature on the band gap and band edges of the hybrid pervoskite CH3NH3PbI3 by accounting for electron-phonon coupling and thermal expansion. From 290 to 380 K, the computed band gap change of 40 meV coincides with the experimental change of 30-40 meV. The calculation of electron-phonon coupling in CH3NH3PbI3 is particularly intricate as the commonly used Allen-Heine-Cardona theory overestimates the band gap change with temperature, and excellent agreement with experiment is only obtained when including high-order terms in the electron-phonon interaction. We also find that spin-orbit coupling enhances the electron-phonon coupling strength but that the inclusion of nonlocal correlations using hybrid functionals has little effect. We reach similar conclusions in the metal-halide perovskite CsPbI3. Our results unambiguously confirm for the first time the importance of high-order terms in the electron-phonon coupling by direct comparison with experiment.

Environmental effects and intrinsic energy-loss processes lead to fluctuations in the operational temperature of solar cells, which can profoundly influence their power conversion efficiency. Here we determine from first principles the effects of temperature on the band gap and band edges of the hybrid pervoskite CH$_3$NH$_3$PbI$_3$ by accounting for electron-phonon coupling and thermal expansion. From $290$ to $380$ K, the computed band gap change of $40$ meV coincides with the experimental change of $30$-$40$ meV. The calculation of electron-phonon coupling in CH$_3$NH$_3$PbI$_3$ is particularly intricate, as the commonly used Allen-Heine-Cardona theory overestimates the band gap change with temperature, and excellent agreement with experiment is only obtained when including high-order terms in the electron-phonon interaction. We also find that spin-orbit coupling enhances the electron-phonon coupling strength, but that the inclusion of nonlocal correlations using hybrid functionals has little effect. We reach similar conclusions in the metal-halide perovskite CsPbI$_3$. Our results unambiguously confirm for the first time the importance of high-order terms in the electron-phonon coupling by direct comparison with experiment., main: 7 pages, 3 figures; supporting information: 8 pages, 8 figures