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Atomic vibrational dynamics in cuprite, Cu2O, was studied by inelastic neutron scattering and molecular dynamics (MD) simulations from 10 K to 900 K. Above 300 K, a diffuse inelastic intensity (DII) appeared, obscuring the high-energy phonon modes. Classical MD simulations with a machine learning interatomic potential reproduced general features of the DII, especially with a Langevin thermostat. The DII originates from random phase shifts of vibrating O-atoms that have anharmonic interactions with neighboring Cu-atoms.

A quantum Langevin model, similar to models used recently for optomechanics, was used to predict intermodulation phonon sidebands (IPS). Ab initio calculations of anharmonic phonons in rocksalt NaBr showed these spectral features as "many-body effects". Modern inelastic neutron scattering measurements on a crystal of NaBr at 300K revealed diffuse intensity at high phonon energy from a predicted upper IPS. The transverse optical (TO) part of the new features originates from phonon intermodulation between the transverse acoustic (TA) and TO phonons. The longitudinal optical (LO) spectral features originate from three-phonon coupling between the TA modes and the TO lattice modes. The partner lower IPS proves to be an "intrinsic localized mode". Interactions with the thermal bath broaden and redistribute the spectral weight of the IPS pair. These sidebands are a probe of anharmonicity and quantum noise, which originate from interactions between the phonons in NaBr.

All phonons in a single crystal of NaBr were measured by inelastic neutron scattering at temperatures of 10, 300 and 700 K. Even at 300 K the phonons, especially the longitudinal-optical (LO) phonons, showed large shifts in frequencies, and showed large broadenings in energy owing to anharmonicity. Ab initio computations were first performed with the quasiharmonic approximation (QHA), in which the phonon frequencies depend only on $V$, and on $T$ only insofar as it alters $V$ by thermal expansion. This QHA was an unqualified failure for predicting the temperature dependence of phonon frequencies, even 300 K, and the thermal expansion was in error by a factor of four. Ab initio computations that included both anharmonicity and quasiharmonicity successfully predicted both the temperature dependence of phonons and the large thermal expansion of NaBr. The frequencies of LO phonon modes decrease significantly with temperature owing to the real part of the phonon self-energy from explicit anhamonicity, originating from the cubic anharmonicity of nearest-neighbor Na-Br bonds. Anharmonicity is not a correction to the QHA predictions of thermal expansion and thermal phonon shifts, but dominates the behavior., Comment: 3 figures, 1 table, and the Supplementary Material appended

Despite the widespread use of silicon in modern technology, its peculiar thermal expansion is not well-understood. Adapting harmonic phonons to the specific volume at temperature, the quasiharmonic approximation, has become accepted for simulating the thermal expansion, but has given ambiguous interpretations for microscopic mechanisms. To test atomistic mechanisms, we performed inelastic neutron scattering experiments from 100-1500K on a single-crystal of silicon to measure the changes in phonon frequencies. Our state-of-the-art ab initio calculations, which fully account for phonon anharmonicity and nuclear quantum effects, reproduced the measured shifts of individual phonons with temperature, whereas quasiharmonic shifts were mostly of the wrong sign. Surprisingly, the accepted quasiharmonic model was found to predict the thermal expansion owing to a fortuitous cancellation of contributions from individual phonons.

Although the rutile structure of TiO$_2$ is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000\,K. Inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO$_2$ from 300 to 1373\,K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of $3d$ electrons of Ti and $2p$ electrons of O atoms. With thermal expansion, the energy variation in this "phonon-tracked hybridization" flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential., Comment: 7 pages, 6 figures, supplemental material (3 figures)

Phonon densities of states (DOS) of bcc $\alpha$-$^{57}$Fe were measured from room temperature through the 1044K Curie transition and the 1185K fcc $\gamma$-Fe phase transition using nuclear resonant inelastic x-ray scattering. At higher temperatures all phonons shift to lower energies (soften) with thermal expansion, but the low transverse modes soften especially rapidly above 700K, showing strongly nonharmonic behavior that persists through the magnetic transition. Interatomic force constants for the bcc phase were obtained by iteratively fitting a Born-von K\'{a}rm\'{a}n model to the experimental phonon spectra using a genetic algorithm optimization. The second-nearest-neighbor fitted axial force constants weakened significantly at elevated temperatures. An unusually large nonharmonic behavior is reported, which increases the vibrational entropy and accounts for a contribution of 35 meV/atom in the free energy at high temperatures. The nonharmonic contribution to the vibrational entropy follows the thermal trend of the magnetic entropy, and may be coupled to magnetic excitations. A small change in vibrational entropy across the $\alpha$-$\gamma$ structural phase transformation is also reported.

We have studied the phonon density of states (PDOS) in LaFeAsO1-xFx with inelastic neutron scattering methods. The PDOS of the parent compound(x=0) is very similar to the PDOS of samples optimally doped with fluorine to achieve the maximum Tc (x~0.1). Good agreement is found between the experimental PDOS and first-principle calculations with the exception of a small difference in Fe mode frequencies. The PDOS reported here is not consistent with conventional electron-phonon mediated superconductivity.

Electron energy-loss spectrometry was employed to measure the white lines at the L23 absorption edges of the 3d transition-metal oxides and lithium transition-metal oxides. The white-line ratio (L3/L2) was found to increase between d^0 and d^5 and decrease between d^5 and d^10, consistent with previous results for the transition metals and their oxides. The intensities of the white lines, normalized to the post-edge background, are linear for the 3d transition-metal oxides and lithium transition-metal oxides. An empirical correlation between normalized white-line intensity and 3d occupancy is established. It provides a method for measuring changes in the 3d-state occupancy. As an example, this empirical relationship is used to measure changes in the transition-metal valences of Li_{1-x}Ni_{0.8}Co_{0.2}O_2 in the range of 0 < x < 0.64. In these experiments the 3d occupancy of the nickel ion decreased upon lithium deintercalation, while the cobalt valence remained constant., Comment: 6 pages, 7 figures