Reentrant valence transition in EuO at high pressures: beyond the bond-valence model.

The pressure-dependent relation between Eu valence and lattice structure in model compound EuO is studied with synchrotron-based x-ray spectroscopic and diffraction techniques. Contrary to expectation, a 7% volume collapse at ≈45 GPa is accompanied by a reentrant Eu valence transition into a lower valence state. In addition to highlighting the need for probing both structure and electronic states directly when valence information is sought in mixed-valent systems, the results also show that widely used bond-valence methods fail to quantitatively describe the complex electronic valence behavior of EuO under pressure.

Elastic relaxations associated with the Pm3m-R3c transition in LaAlO(3): I. Single crystal elastic moduli at room temperature.

Values for all six independent components of the 3m elastic modulus tensor of LaAlO(3) perovskite are reported. These were determined by means of Brillouin scattering measurements of acoustic velocities in single crystal plates cut parallel to (110) and (100), as defined with respect to the cubic parent structure, and by pure-mode longitudinal and transverse sound velocity measurements along [100], [110] and [111] directions using GHz pulse-echo ultrasonics. The crystals contained intimate intergrowths of twins arising from the Pm3m <--> R3c transition at higher temperature but, in combination with a careful analysis of twin orientation relationships, the two sets of data have allowed a unique solution to be obtained for individual twin components. The new data set represents an important contribution to the characterization of LaAlO(3) single crystals which are widely used as the substrate for a plethora of different thin films with technological applications.

Elastic relaxations associated with the Pm3m-R3c transition in LaAlO(3): II. Mechanisms of static and dynamical softening.

Brillouin spectra have been collected in situ at temperatures up to ∼1000 K for different crystallographic directions from two single crystal plates of LaAlO(3) perovskite. Elastic moduli derived from these, together with heat capacity, spontaneous strain and Raman data from the literature, have then been used to calibrate the coefficients in a classical Landau free energy expansion for the second order [Formula: see text] phase transition at T(c) = 817 K. The static strain/order parameter coupling model provides a quantitative description of elastic softening between room temperature and ∼700 K, but from ∼700 K up to T(c) additional elastic softening correlates with the development of a central peak in the Brillouin spectra. The presence of quasi-elastic scattering, which reaches maximum intensity ∼5-15 K below T(c), implies a strong dynamical component to the phase transition. Relaxation times estimated from the width of the central peak are of the order of ∼10-100 ps and appear to be more or less constant between ∼700 and 800 K, which is consistent with an intrinsic origin associated with phonon density fluctuations. Central peak width variations and an irregular pattern of acoustic velocity variations in a 20 K temperature interval below T(c) are interpreted in terms of flipping of clusters of tilted octahedra between different ⟨111⟩, ⟨011⟩ and ⟨001⟩ tilt axes. The additional softening beyond that expected from the classical strain/order parameter coupling model can be understood in terms of coupling of acoustic modes with the central peak mode(s).