Soft phonon modes in rutile TiO2_2

The lattice dynamics of TiO$_2$ in the rutile crystal structure was studied by a combination of thermal diffuse scattering, inelastic x-ray scattering and density functional perturbation theory. We experimentally confirm the existence of an anomalous soft transverse acoustic mode with energy minimum at q = (1/2 1/2 1/4). The phonon energy landscape of this particular branch is reported and compared to the calculation. The harmonic calculation underestimates the phonon energies but despite this the shape of both the energy landscape and the scattering intensities are well reproduced. We find a significant temperature dependence in energy of this transverse acoustic mode over an extended region in reciprocal space which is in line with a substantially anharmonic mode potential-energy surface. The reported low energy branch is quite different from the ferroelectric mode that softens at the Brillouin zone center and may help explain anomalous convergence behavior in calculating TiO$_2$ surface properties

Anharmonicity and structural phase transition in the Mott insulator Cu2_2P2_2O7_7

Ab initio investigations of structural, electronic, and dynamical properties of the high-temperature $\beta$ phase of copper pyrophosphate were performed using density functional theory. The electronic band structure shows the Mott insulating state due to electron correlations in copper ions. By calculating phonon dispersion relations, the soft mode at the A point of the Brillouin zone was revealed, showing the dynamical instability of the $\beta$ phase at low temperatures. The double-well potential connected with the soft mode is derived and the mechanism of the structural phase transition to the $\alpha$ phase is discussed. The self-consistent phonon calculations based on the temperature-dependent effective potential show the stabilization of the $\beta$ phase at high temperatures, due to the anharmonic effects. The pronounced temperature dependence and the large line width of the soft mode indicate an essential role of anharmonicity in the structural phase transition

Influence of anharmonicity on the negative thermal expansion of α−Sn\alpha-Sn

The lattice vibrational properties of $\alpha-Sn$ (gray tin) were investigated experimentally by temperature-dependent x-ray diffraction and theoretically by density functional theory calculations. Similar to the other elements of group IV, $\alpha-Sn$ exhibits a lattice anomaly at low temperatures and negative thermal expansion, with a minimum at $\sim 27K$ and a magnitude three times larger than in Si. The influence of anharmonic effects up to fourth-order potential terms on the phonon dispersion relations, the lattice parameters, and the thermal expansion coefficient have been tested. The performed analysis gives an excellent agreement with experiment when quartic potential terms are included in the theory. We point out that negative thermal expansion in $\alpha-Sn$ is not driven by the anharmonicity of the interatomic potential. This resolves the long-standing puzzle in the thermal behavior of $\alpha-Sn$

Structure and elastic properties of Mg(OH)2_2 from density functional theory

The structure, lattice dynamics and mechanical properties of the magnesium hydroxide have been investigated with static density functional theory calculations as well as \it {ab initio} molecular dynamics. The hypothesis of a superstructure existing in the lattice formed by the hydrogen atoms has been tested. The elastic constants of the material have been calculated with static deformations approach and are in fair agreement with the experimental data. The hydrogen subsystem structure exhibits signs of disordered behaviour while maintaining correlations between angular positions of neighbouring atoms. We establish that the essential angular correlations between hydrogen positions are maintained to the temperature of at least 150 K and show that they are well described by a physically motivated probabilistic model. The rotational degree of freedom appears to be decoupled from the lattice directions above 30K

Phonon confinement and interface lattice dynamics of ultrathin high-rare earth sesquioxide films: the case of Eu₂O₃ on YSZ(001)

The spatial confinement of atoms at surfaces and interfaces significantly alters the lattice dynamics of thin films, heterostructures and multilayers. Ultrathin films with high dielectric constants (high-k) are of paramount interest for applications as gate layers in current and future integrated circuits. Here we report a lattice dynamics study of high-k Eu$_{2}$O$_{3}$ films with thicknesses of 21.3, 2.2, 1.3, and 0.8 nm deposited on YSZ(001). The Eu-partial phonon density of states (PDOS), obtained from nuclear inelastic scattering, exhibits broadening of the phonon peaks accompanied by up to a four-fold enhancement of the number of low-energy states compared to the ab initio calculated PDOS of a perfect Eu$_{2}$O$_{3}$ crystal. Our analysis demonstrates that while the former effect reflects the reduced phonon lifetimes observed in thin films due to scattering from lattice defects, the latter phenomenon arises from an ultrathin EuO layer formed between the thin Eu$_{2}$O$_{3}$ film and the YSZ(001) substrate. Thus, our work uncovers another potential source of vibrational anomalies in thin films and multilayers, which has to be cautiously considered

Phononic drumhead surface state in the distorted kagome compound RhPb

RhPb was initially recognized as one of CoSn-like compounds with P6/mmm symmetry, containing an ideal kagome lattice of d-block atoms. However, theoretical calculations predict the realization of the phonon soft mode, which leads to the kagome lattice distortion and stabilization of the structure with P$\bar{6}$2m symmetry [A. Ptok et al., Phys. Rev. B 104, 054305 (2021)]. Here, we present the single crystal x-ray diffraction results supporting this prediction. Furthermore, we discuss the main dynamical properties of RhPb with P$\bar{6}$2m symmetry, i.e. phonon dispersions and surface Green's functions using the modern theoretical methods based on density functional theory. The bulk phononic dispersion curves contain several flattened bands, Dirac nodal lines, and triple degenerate Dirac points. As a consequence, the phononic drumhead surface state is realized for the (100) surface, terminated by the zigzaglike edge of Pb honeycomb sublattice