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We give here the exact expression of the time dependent third order polarization predicted by the "box model" when a supercooled liquid is permanently subjected since time t = 0 to a strong electric field E(t) = E0 sin(ωt) , Dielectric Hole Burning experiment. We derive different forms of the time dependent susceptibilities, both at frequencies ω and 3ω, and examine particularly one of them. We also show that its susceptibility at ω should exhibit, at short times, presently undetected oscillations at frequency 2ω that are a signature of the "box model." We finally compare, for a large frequency range, the ω and 3ω time independent susceptibilities with the corresponding measurements on glycerol at 204.7 K. The agreement is good at frequency ω but, as already shown in Ladieu et al. [J. Chem. Phys. 134, 194507 (2011)], it is not the case at 3ω. [ABSTRACT FROM AUTHOR]

We present results of a series of experiments performed on LiBr, 6H20 from room temperature down to 172 K ≈ 1.2Tg. These ultrasound, Brillouin and depolarized light scattering, and transient grating experiments show that, above 215 K, this solution behaves like supercooled water: its zero frequency sound velocity C0 continuously decreases with decreasing temperature, and the reorientational dynamics of the water molecules can be directly detected at some temperatures of this domain. Conversely, below 215 K, a new regime sets in, where the apparent C0 is practically temperature independent and where a β, Arrenhius like, relaxation process coexists with the usual, Vogel-Fulcher like, α relaxation process of the supercooled liquid. These results are similar to those recently obtained in LiCl, 6H2O. The onset of the new regime is possibly due to an increase of the interaction of the water molecules with a neighboring Li+ ion when lowering the temperature. We also compare our results with published dielectric data on water solutions of glass forming polyalcohols. Some of them present a low temperature splitting of their relaxation time similar to what is found in LiBr, 6H2O. [ABSTRACT FROM AUTHOR]

We report the results of a series of ultrasound, Brillouin scattering, and optical heterodyne detected transient grating experiments performed on a LiCl, 6H2O solution from room temperature down to the vicinity of its liquid-glass transition, Tg∼138 K. Down to T∼215 K, the supercooled liquid has a behavior similar to what is expected for supercooled water: its zero frequency sound velocity, C0, continuously decreases while the corresponding infinite frequency velocity, C∞, sharply increases, reflecting the increasing importance of H bonding when temperature is lowered. Below 215 K, specific aspects of the solution, presumably related to the role of the Li+ and Cl- ions, modify the thermal behavior of C0, while a β relaxation process also appears and couples to the sound propagation. The origin of those two effects is briefly discussed. [ABSTRACT FROM AUTHOR]

Prigogine–Defay ratios and, more recently, their frequency extension have been proposed to be a measure of the number of nonmacroscopic processes involved in the relaxation dynamics of supercooled liquids. We show that the microscopic theory of the Navier–Stokes equations of those liquids provides a consistent thermodynamic framework in which all possible dynamical Prigogine–Defay ratios can be expressed in terms of the same relaxation functions and that these ratios provide less information than the microscopic theory itself. The latter shows that more than one relaxation process is certainly always involved in this relaxation dynamics, whatever is the molecular dynamics, or experimental, technique used to determine the latter. [ABSTRACT FROM AUTHOR]

We present here the calculation of the "time dependent" moduli of the third order, dielectric, susceptibilities measured at the frequency ω of the applied electric field and at the frequency 3ω. The calculation is performed within the frame work of the "box model," both in the ideal case of a pure third order polarization and in the practical case studied by Samanta and Richert [J. Chem. Phys. 140, 247101 (2014)] where a first order polarization contribution is also detected. We show that, in the two cases, those two modules have a largely different dynamics and that the results can be easily compared with experiments thanks to the data gathered by Samanta and Richert [J. Chem. Phys. 140, 247101 (2014)]. This should provide a new test on the validity of the "box model." [ABSTRACT FROM AUTHOR]

A molecular dynamics simulation of a realistic model of neopentane [C(CH3)4] in its plastic phase has been performed on a sample of 6×6×6 fcc unit cells (i.e., 864 molecules) at 135, 175, and 230 K. The molecules of the simulated sample interact through phenomenological exp-6, atom–atom potentials between all the atoms of nearest neighbor molecules. The orientational probability density function (opdf), the displacement probability density function (dpdf), and its second moment the Debye–Waller factor have been computed. We confirm the very large value and the important thermal variation of the Debye–Waller factor and the strong anisotropy of the opdf deduced from neutron diffraction experiments. The computed opdf is very well reproduced by a mean-field calculation making use only of the microscopic intermolecular potential and of the equilibrium position of the molecular centers of mass, a result in line with the isotropic character of the dpdf, but not valid for other plastic crystals made of molecules with different geometries. [ABSTRACT FROM AUTHOR]

We present the results of a numerical study of the effects of the induced dipole–induced dipole interaction on the line shape of the internal ν1 and ν3 modes of NF3 in the plastic phase. Comparisons are made both with the experiment and with the results of a previous theoretical analysis of the effect. [ABSTRACT FROM AUTHOR]

The systematic development of the harmonic, intermolecular, internal mode interaction energy in terms of symmetry adapted Wigner functions of the molecular orientations is given for a plastic crystal. This development is used for the study of the Raman profile of a mode with a strong induced dipole-induced dipole interaction between the vibrating molecules. An approximate form of the profile is proposed, and compared with measurements made on NF3 by Gilbert and Nectoux. [ABSTRACT FROM AUTHOR]

A response from the author of the article "Third order susceptibilities in supercooled liquids and the "box model" theory versus experiments" in the June 27, 2014 issue is presented.

Transient grating experiments performed on supercooled LiCl, RH2O solutions with R > 6 reveal the existence of well resolved, short time, extra signal which superposes to the normal signal observed for the R = 6 solution and for homogenous glass forming systems. This extra signal shows up below 190 K, its shape and the associated timescale depend only on temperature, while its intensity increases with R. We show that the origin of this signal is a phase separation between clusters with a low solute concentration and the remaining, more concentrated, solution. Our analysis demonstrates that these clusters have a nanometer size and a composition which are rather temperature independent, while increasing R simply increases the density of these clusters. [ABSTRACT FROM AUTHOR]

An experimental study of the glass transition of meta-toluidine combining several light scattering techniques was performed. The structural relaxation time is measured in depolarized geometry from the glass transition temperature up to well above the melting point and found to vary over 13 time decades. An analysis by means of the idealized Mode Coupling Theory shows that, as found in other aromatic liquids, experimental results obtained in depolarized light scattering can be described by this theory above T[sub c] in a two-decade frequency range. The polarized Brillouin doublet, measured in the backscattering geometry between 176 K and 300 K, is also analyzed. None of the sets of parameters we obtained in fitting those spectra could fulfil all the requirements of this Mode Coupling Theory. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report the results of a series of ultrasound, Brillouin scattering, and optical heterodyne detected transient grating experiments performed on a LiCl, 6H(2)O solution from room temperature down to the vicinity of its liquid-glass transition, T(g) approximately 138 K. Down to T approximately 215 K, the supercooled liquid has a behavior similar to what is expected for supercooled water: its zero frequency sound velocity, C(0), continuously decreases while the corresponding infinite frequency velocity, C(infinity), sharply increases, reflecting the increasing importance of H bonding when temperature is lowered. Below 215 K, specific aspects of the solution, presumably related to the role of the Li(+) and Cl(-) ions, modify the thermal behavior of C(0), while a beta relaxation process also appears and couples to the sound propagation. The origin of those two effects is briefly discussed.