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In the prevalent picture of ultrafast structural phase transitions, the atomic motion occurs in a slowly varying potential energy surface determined adiabatically by the fast electrons. However, this ignores non-conservative forces caused by electron-lattice collisions, which can significantly influence atomic motion. Most ultrafast techniques only probe the average structure and are less sensitive to random displacements, and therefore do not detect the role played by non-conservative forces in phase transitions. Here we show that the lattice dynamics of the prototypical insulator-to-metal transition of VO2 cannot be described by a potential energy alone. We use the sample temperature to control the preexisting lattice disorder before ultrafast photoexcitation across the phase transition and our ultrafast diffuse scattering experiments show that the fluctuations characteristic of the rutile metal develop equally fast (120 fs) at initial temperatures of 100 K and 300 K. This indicates that additional non-conservative forces are responsible for the increased lattice disorder. These results highlight the need for more sophisticated descriptions of ultrafast phenomena beyond the Born-Oppenheimer approximation as well as ultrafast probes of spatial fluctuations beyond the average unit cell measured by diffraction.

Ion transport across solid solid interfaces is often slower than through the bulk of a material, impeding the charge and discharge rate of batteries. Designing highly conductive interfaces is challenging due to the need to probe ion conduction at individual interfaces and correlate it with the local structure. In this study, we address this challenge by enabling the simultaneous measurements of local Li-dominated optical phonons and ion distributions, using high-energy and high-spatial-resolution spectroscopy in a scanning transmission electron microscope (STEM). Further, this method allows for a direct correlation of ion conduction with interfacial structures identified by STEM imaging. By examining diverse individual interfaces of LiCoO2, we reveal the sensitivity of ion conduction to interface atomic-scale structure and chemistry. Our method enables correlative analysis of ion transport behavior, and atomic and band structures, and can serve as a robust experimental approach for identifying interface structures that offer high conductivity and cyclability for batteries.

Interatomic forces that bind materials are largely determined by an often complex interplay between the electronic band-structure and the atomic arrangements to form its equilibrium structure and dynamics. As these forces also determine the phonon dispersion, lattice dynamics measurements are often crucial tools for understanding how materials transform between different structures. This is the case for the mono-chalcogenides which feature a number of lattice instabilities associated with their network of resonant bonds and a large tunability in their functional properties. SnSe hosts a novel lattice instability upon above-bandgap photoexcitation that is distinct from the distortions associated with its high temperature phase transition, demonstrating that photoexcitation can alter the interatomic forces significantly different than thermal excitation. Here we report decisive time-resolved X-ray scattering-based measurements of the nonequlibrium lattice dynamics in SnSe. By fitting interatomic force models to the excited-state dispersion, we determine this instability as being primarily due to changes in the fourth-nearest neighbor bonds that connect bilayers, with relatively little change to the intralayer resonant bonds. In addition to providing critical insight into the nonthermal bonding origin of the instability in SnSe, such measurements will be crucial for understanding and controlling materials properties under non-equilibrium conditions.

Spin and lattice are two fundamental degrees of freedom in a solid, and their fluctuations about the equilibrium values in a magnetic ordered crystalline lattice form quasiparticles termed magnons (spin waves) and phonons (lattice waves), respectively. In most materials with strong spin-lattice coupling (SLC), the interaction of spin and lattice induces energy gaps in the spin wave dispersion at the nominal intersections of magnon and phonon modes. Here we use neutron scattering to show that in the two-dimensional (2D) van der Waals honeycomb lattice ferromagnetic CrGeTe3, spin waves propagating within the 2D plane exhibit an anomalous dispersion, damping, and break-down of quasiparticle conservation, while magnons along the c axis behave as expected for a local moment ferromagnet. These results indicate the presence of dynamical SLC arising from the zero-temperature quantum fluctuations in CrGeTe3, suggesting that the observed in-plane spin waves are mixed spin and lattice quasiparticles fundamentally different from pure magnons and phonons., Comment: 12 pages, 4 figures; Nature Communication in press

Cu2Se and Cu2S are excellent model systems of superionic conductors with large diffusion coefficients that have been reported to exhibit different solid-liquid-like Cu-ion diffusion. In this paper, we clarify the atomic dynamics of these compounds with temperature-dependent ab-initio molecular dynamics (AIMD) simulations and inelastic neutron scattering (INS) experiments. Using the dynamical structure factor and Van-Hove correlation function, we interrogate the jump-time, hopping length distribution and associated diffusion coefficients. In cubic-Cu2Se at 500 K, we find solid-like diffusion with Cu-jump lengths matching well the first-neighbour Cu-Cu distance of ~3 {\AA} in the crystal, and clearly defined optic phonons involving Cu-vibrations. Above 700 K, the jump-length distribution becomes a broad maximum cantered around 4 {\AA}, spanning the first and second neighbour lattice distances, and a concurrent broadening of the Cu-phonon density of states. Further, above 900 K, the Cu-diffusion becomes close to liquid-like, with distributions of Cu-atoms continuously connecting crystal sites, while the vibrational modes involving Cu motions are highly damped, though still not fully over-damped as in a liquid. At low temperatures, the solid-like diffusion is consistent with previous X-ray diffraction and quasielastic neutron scattering experiments, while the higher-temperature observation of the liquid-like diffusion is in agreement with previous AIMD simulations. We also report AIMD simulations in Cu2S in the hexagonal and cubic superionic phases, and observe similar solid and liquid-like diffusion at low- and high-temperatures, respectively. The calculated ionic-conductivity is in fair agreement with reported experimental values., Comment: 29 Pages, 7 Figures

Metal halides perovskites (MHPs) are attracting considerable interest for optoelectronic applications, with Cs$_2$AgBiBr$_6$ one of the main contenders among lead-free systems. Cs$_2$AgBiBr$_6$ crystallizes in a nominally double-perovskite structure, but exhibits a soft lattice with large atomic fluctuations characteristic of MHPs. While crucial to understand electron-phonon and phonon-phonon couplings, the spatio-temporal correlations of these fluctuations remain largely unknown. Here, we reveal these correlations using comprehensive neutron and x-ray scattering measurements on Cs$_2$AgBiBr$_6$ single-crystals, complemented with first-principles simulations augmented with machine-learned neural-network potentials. We report the discovery of an unexpected complex modulated ground state structure containing several hundred atoms, arising from a soft-phonon instability of the low-temperature tetragonal phase. Further, our experiments and simulations both reveal extensive correlated 2D fluctuations of Br octahedra at finite temperature, arising from soft anharmonic optic phonons, reflecting very shallow potential wells. These results provide new insights into the atomic structure and fluctuations in MHPs, critical to understand and control their thermal and optoelectronic properties., Comment: 12 pages, 4 figures

We report on investigations of phonons and lithium diffusion in LiAlO$_2$ based on inelastic neutron scattering (INS) measurements of the phonon density of states (DOS) in {\gamma}-LiAlO$_2$ from 473 K to 1073 K, complemented with ab-initio molecular dynamics (AIMD) simulations. We find that phonon modes related to Li vibrations broaden on warming as reflected in the measured phonon DOS and reproduced in simulations. Further, the AIMD simulations probe the nature of lithium diffusion in the perfect crystalline phase ({\gamma}-LiAlO$_2$), as well as in a structure with lithium vacancies and a related amorphous phase. Almost liquid-like super-ionic diffusion is observed in AIMD simulations of the three structures at high temperatures; with predicted onset temperatures of 1800 K, 1200 K, and 600 K in the perfect structure, vacancy structure and the amorphous phase, respectively. In the ideal structure, the Li atoms show correlated jumps; while simple and correlated jumps are both seen in the vacancy structure, and a mix of jumps and continuous diffusion occur in the amorphous structure. Further, we find that the Li-diffusion is favored in all cases by a large librational amplitude of the neighbouring AlO4 tetrahedra, and that the amorphous structure opens additional diffusion pathways due to a broad distribution of AlO4 tetrahedra orientations., Comment: 31 Pages, 14 figures

The anharmonic phonon properties of SnSe in the Pnma phase were investigated with a combination of experiments and first-principles simulations. Using inelastic neutron scattering (INS) and nuclear resonant inelastic X-ray scattering (NRIXS), we have measured the phonon dispersions and density of states (DOS) and their temperature dependence, which revealed a strong, inhomogeneous shift and broadening of the spectrum on warming. First-principles simulations were performed to rationalize these measurements, and to explain the previously reported anisotropic thermal expansion, in particular the negative thermal expansion within the Sn-Se bilayers. Including the anisotropic strain dependence of the phonon free energy, in addition to the electronic ground state energy, is essential to reproduce the negative thermal expansion. From the phonon DOS obtained with INS and additional calorimetry measurements, we quantify the harmonic, dilational, and anharmonic components of the phonon entropy, heat capacity, and free energy. The origin of the anharmonic phonon thermodynamics is linked to the electronic structure., Comment: 14 pages, 12 figures

Intriguing lattice dynamics has been predicted for aperiodic crystals that contain incommensurate substructures. Here we report inelastic neutron scattering measurements of phonon and magnon dispersions in Sr14Cu24O41, which contains incommensurate one-dimensional (1D) chain and two-dimensional (2D) ladder substructures. Two distinct pseudoacoustic phonon modes, corresponding to the sliding motion of one sublattice against the other, are observed for atomic motions polarized along the incommensurate axis. In the long wavelength limit, it is found that the sliding mode shows a remarkably small energy gap of 1.7-1.9 meV, indicating very weak interactions between the two incommensurate sublattices. The measurements also reveal a gapped and steep linear magnon dispersion of the ladder sublattice. The high group velocity of this magnon branch and weak coupling with acoustic and pseudoacoustic phonons can explain the large magnon thermal conductivity in Sr14Cu24O41 crystals. In addition, the magnon specific heat is determined from the measured total specific heat and phonon density of states, and exhibits a Schottky anomaly due to gapped magnon modes of the spin chains. These findings offer new insights into the phonon and magnon dynamics and thermal transport properties of incommensurate magnetic crystals that contain low-dimensional substructures.

The binary compound SnSe exhibits record high thermoelectric performance, largely because of its very low thermal conductivity. The origin of the strong phonon anharmonicity leading to the low thermal conductivity of SnSe is investigated through first-principles calculations of the electronic structure and phonons. It is shown that a Jahn-Teller instability of the electronic structure is responsible for the high-temperature lattice distortion between the Cmcm and Pnma phases. The coupling of phonon modes and the phase transition mechanism are elucidated, emphasizing the connection with hybrid improper ferroelectrics. This coupled instability of electronic orbitals and lattice dynamics is the origin of the strong anharmonicity causing the ultralow thermal conductivity in SnSe. Exploiting such bonding instabilities to generate strong anharmonicity may provide a new rational to design efficient thermoelectric materials.

Based on thermodynamic principles, we derive expressions quantifying the non-harmonic vibrational behavior of materials, which are rigorous yet easily evaluated from experimentally available data for the thermal expansion coefficient and the phonon density of states. These experimentally- derived quantities are valuable to benchmark first-principles theoretical predictions of harmonic and non-harmonic thermal behaviors using perturbation theory, ab initio molecular-dynamics, or Monte-Carlo simulations. We illustrate this analysis by computing the harmonic, dilational, and anharmonic contributions to the entropy, internal energy, and free energy of elemental aluminum and the ordered compound FeSi over a wide range of temperature. Results agree well with previous data in the literature and provide an efficient approach to estimate anharmonic effects in materials., Comment: 8 pages, 6 figures

Phonon properties of $\mathrm{Mo_3Sb_{7-x}Te_x}$ ($x=0,1.5, 1.7$), a potential high-temperature thermoelectric material, have been studied with inelastic neutron and x-ray scattering, and with first-principles simulations. The substitution of Te for Sb leads to pronounced changes in the electronic structure, local bonding, phonon density of states (DOS), dispersions, and phonon lifetimes. Alloying with tellurium shifts the Fermi level upward, near the top of the valence band, resulting in a strong suppression of electron-phonon screening, and a large overall stiffening of interatomic force-constants. The suppression in electron-phonon coupling concomitantly increases group velocities and suppresses phonon scattering rates, surpassing the effects of alloy-disorder scattering, and resulting in a surprising increased lattice thermal conductivity in the alloy. We also identify that the local bonding environment changes non-uniformly around different atoms, leading to variable perturbation strengths for different optical phonon branches. The respective roles of changes in phonon group velocities and phonon lifetimes on the lattice thermal conductivity are quantified. Our results highlight the importance of the electron-phonon coupling on phonon mean-free-paths in this compound, and also estimates the contributions from boundary scattering, umklapp scattering, and point-defect scattering., Comment: 16 pages, 13 figures

The origin of the anomalous anharmonic lattice dynamics of lead telluride is investigated using molecular dynamics simulations with interatomic force constants (IFCs) up to quartic terms obtained from first principles. The calculations reproduce the peak asymmetry of the radial distribution functions and the double peaks of transverse optical phonon previously observed with neutron diffraction and scattering experiments. They are identified to be due to the extremely large nearest-neighbor cubic IFCs in the [100] direction. The outstanding strength of the nearest-neighbor cubic IFCs relative to the longer-range ones explains the reason why the distortion in the radial distribution function is local.

The microscopic physics behind low lattice thermal conductivity of single crystal rocksalt lead telluride (PbTe) is investigated. Mode-dependent phonon (normal and umklapp) scattering rates and their impact on thermal conductivity were quantified by the first-principles-based anharmonic lattice dynamics calculations that accurately reproduce thermal conductivity in a wide temperature range. The low thermal conductivity of PbTe is attributed to the scattering of longitudinal acoustic phonons by transverse optical phonons with large anharmonicity, and small group velocity of the soft transverse acoustic phonons. This results in enhancing the relative contribution of optical phonons, which are usually minor heat carrier in bulk materials., Comment: 18 pages, 4 figures, accepted for publication in Phys. Rev. B

Single crystals of CaZn2Sb2, EuZn2Sb2, and YbZn2Sb2 were grown from melts of nominal composition AZn5Sb5 (A=Ca,Eu,Yb) with the excess melt being removed at 1073\,K. The electrical transport properties are consistent with those previously reported for polycrystalline samples. This confirms that the $p$-type carrier concentrations ranging from 2x10^{19}cm^{-3} to ~1x10^{20}cm^{-3} are intrinsic to these materials. Also consistent with transport in polycrystalline materials, the carrier mobility is found to be lowest in CaZn2Sb2, suggesting the trends in mobility and thermoelectric efficiency within these compounds are inherent to the material systems and not due to inhomogeneity or impurities in polycrystalline samples. These results suggest CaZn2Sb2 has the strongest coupling between the doping/defects and the electronic framework. Magnetization measurements reveal an antiferromagnetic transition near 13\,K in EuZn2Sb2, and the observed magnetic anisotropy indicates the spins align parallel and anti-parallel to $c$ in the trigonal lattice. Powder neutron diffraction on polycrystalline samples of CaZn2Sb2 and YbZn2Sb2 reveals smooth lattice expansion to 1000\,K, with $c$ expanding faster than $a$. The Debye temperatures calculated from specific heat capacity data and the isotropic displacement parameters are found to correlate with the carrier mobility, with the CaZn2Sb2 displaying the largest Debye temperature and smallest mobility., Comment: Copyright (2012) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in (J. Appl. Phys. 111, 033708 (2012)) and may be found at http://link.aip.org/link/?JAP/111/033708

The phonon density of states (DOS) and magnetic excitation spectrum of polycrystalline BiFeO$_3$ were measured for temperatures $200 \leq T \leq 750\,$K, using inelastic neutron scattering (INS). Our results indicate that the magnetic spectrum of BiFeO$_3$ closely resembles that of similar Fe perovskites, such as LaFeO$_3$, despite the cycloid modulation in BiFeO$_3$. We do not find any evidence for a spin gap. A strong $T$-dependence of the phonon DOS was found, with a marked broadening of the whole spectrum, providing evidence of strong anharmonicity. This anharmonicity is corroborated by large-amplitude motions of Bi and O ions observed with neutron diffraction. These results highlight the importance of spin-phonon coupling in this material.

The effects of various transition metal dopants on the electrical and thermal transport properties of Fe1-xMxSi alloys (M= Co, Ir, Os) are reported. The maximum thermoelectric figure of merit ZTmax is improved from 0.007 at 60 K for pure FeSi to ZT = 0.08 at 100 K for 4% Ir doping. A comparison of the thermal conductivity data among Os, Ir and Co doped alloys indicates strong electron-phonon coupling in this compound. Because of this interaction, the common approximation of dividing the total thermal conductivity into independent electronic and lattice components ({\kappa}Total = {\kappa}electronic + {\kappa}lattice) fails for these alloys. The effects of grain size on thermoelectric properties of Fe0.96Ir0.04Si alloys are also reported. The thermal conductivity can be lowered by about 50% with little or no effect on the electrical resistivity or Seebeck coefficient. This results in ZTmax = 0.125 at 100 K, still about a factor of five too low for solid-state refrigeration applications.