This paper presents a survey of soft modes and their relationship to structural phase transitions. After introducing the concept of a soft mode, the origin of softening is considered from a lattice-dynamical point. The Landau theory approach to structural transitions is then discussed, followed by a generalization of the soft-mode concept through the use of the dynamic order-parameter susceptibility. The hyper-Raman spectra in the cubic phase of (Ba0.8Sr0.2)Ti-0.95(Zn1/3Nb2/3)(0.05)O-3 are studied with special emphasis on the lowest-frequency phonon mode. The spectral structure is found to change above the Curie temperature (303-873 K). Soft modes were put forward by Cochran and Anderson about 50 years ago as an explanation of structural phase transitions. Extending Landau's theory of phase transitions, their prediction was that the square of the frequency of the soft mode was proportional omega(0)(T)= C root T-T-C where T-c is the transition temperature.

High-pressure polarized Raman spectra of vitreous silica are measured up to 8 GPa in a diamond-anvil cell at room temperature. The combined use of either a non-penetrating pressurizing medium, argon, or a penetrating one, helium, allows to separate density from stress effects on the Raman frequencies. In the framework of a simple central force model, the results emphasize the distinct role played by the shrinkage of the inter-tetrahedral angle Si-O-Si and the force-constant stiffening during the compression. The polarization analysis further reveals the existence of an additional isotropic component in the high frequency wing of the Boson peak. The pressure dependence of the genuine Boson peak frequency is found to be much weaker than previously reported and even goes through a minimum around 2 GPa in a remarkable coincidence with the anomalous compressibility maximum of silica.

We investigate vitreous silica pressurized under the noble gases, He, Ne and Ar by both spectroscopic techniques and numerical simulations. We find an unexpectedhuge solubility of He and Ne at high pressure together with a large decrease of the static compressibility. We show that this relates to the open and flexible structure of the glass allowing gas atoms to distend the network, the same way a porous material deform upon fluid adsorption. This behavior can be rationalized using generalized poromechanical constitutive equations. Direct optical microscopy observations highlight the swelling of the silica network upon fluid adsorption. Very sharp diffusion front of the fluid into the silica the sample is further observed indicating non trivial kinetics of the diffusing atoms. In the Ne case, adsorption-desorption kinetics canbe tracked by Brillouin spectroscopy.

Raman spectroscopy is one of the key experimental methods for the structuralanalysis of glasses, thanks to its simple application and its sensitivity to variations ofcomposition or atomic-scale order. However, the inherent disorder of the glassystructure results to broad and overlapping peaks in the spectra, rendering theirquantitative analysis a challenging task and resulting in a mostly phenomenologicalinterpretation. This drawback can be addressed by the use of modern and accuratetheoretical tools, such as ab-initio vibrational spectroscopies. In this work we havestudied three simple sodosilicate glasses, prepared using a combined classical/ab-initio approach. For these structures, we have used density functional theory (DFT) tocalculate their vibrational density of states, as well as their Raman and IR spectra.The main advantage of the DFT calculations is that the resulting spectra can bedirectly correlated with the structural models and, most importantly, the vibrationalspectrum can be decomposed into exact contributions arising from individualstructural units. In the case of the sodosilicate glasses, we have identifiedcorrelations between spectral characteristics and stoichiometry, the effect of thepresence of bridging and non-bridging oxygens, the contributions of smaller or largerSi-O-Si angles, as well as the ones arising from the presence of the so-called Q-species. These results open the way for the study of even more complex glasses andaid in the interpretation of experimental spectra.

The dynamics of glass forming liquids shows a tremendous slowing down if temperature is decreased: Relaxation times, transport coefficients such as the diffusion constant or the shear viscosity grow by more than 15 orders of magnitude within narrow temperature range. One of the central goals in the field of glass physics is to understand the origin of this dramatic slowing down of the dynamics.There are several scenarios that seem to be able to explain the slowing down of the dynamics and the low temperature state of the glass former. A very popular one is to rationalize the slow dynamics by invoking the existence of a thermodynamic transition, the so-called ideal glass transition from the liquid to an ideal glass states. This ideal glass transition occurs when the configurational entropy, defined as the logarithm of the number of available states, becomes zero. Due to thissingular behavior of the configurational entropy, the relaxation time andtransport coefficients diverge if the transition point is approached [1].However, confirming the existence of the ideal glass transition is a verydifficult task since in practice the system falls out of equilibriumbefore reaching this putative ideal glass transition temperature,thus making the test of this theory most difficult. Furthermore, otherscenarios are also able to explain the slow dynamics without resortingany thermodynamic transition [2].In the present study, we investigate the existence of the idealglass transition by using computer simulation of a canonical binaryLennard-Jones glass former in three dimensions. Massive computationaleffort and efficient sampling algorithm (parallel tempering) allow us toreach equilibrium states that are very deeply supercooled. By measuringthe configurational entropy directly (obtained via thermodynamicintegration), we find that the configuration entropy does not go to zeroat a finite temperature. This implies that the thermodynamic singularityis indeed avoided before reaching a putative ideal glass transitiontemperature predicted by previous studies. Our results indicates thatcontrary to the previous results the system remains in a liquid statedown to zero temperature without showing an ideal glass transition.Furthermore, we analyze the microscopic structure and the potentialenergy landscape of the system to clarify the mechanism that leads tothe avoidance of the ideal glass transition. We find that locallyfavored structures present in the liquid state hardly change in thetemperature range we consider, which rules out another possibility forthe slow dynamics, e.g. the transformation between two distinct liquids,so-called liquid-liquid transition [3]. Instead, we find the potentialenergy landscape contains extensive number of minima even very lowtemperature, which rationalize the avoided singularity.Our results support a theoretical argument that the ideal glasstransition can not exist at bulk system in finite dimensions [5].[1] Adam G and Gibbs JH, J. Chem. Phys., 43, 139 (1965)[2] Chandler D and Garrahan JP, Annu. Rev. Phys. Chem., 61, 191 (2010)[3] Speck T, Royall CP, and Williams SR, arXiv:1409.0751, (2014)[4] Saksaengwijit A and Heuer A, Phys. Rev. Lett., 93, 235701 (2004)[5] Stillinger FH, J. Chem. Phys., 88, 7818 (1988)

No abstract available