Metallic glass-formers in 2D exhibit the same scaling as in 3D between vibrational dynamics and structural relaxation.

Glass-forming systems approaching their glass transition exhibit universal correlations between picosecond vibrational dynamics and long-time structural relaxation, which can be described by the same master curve in the bulk or confined conditions. In this work, we study at a fundamental level the effects of the reduction of spatial dimensionality on this phenomenon. We perform molecular dynamics simulations of a metallic glass-formers in two dimensions (2D). We show that in the supercooled regime particle localization in the cage and structural relaxation are blurred by long-wavelength fluctuations specific to low-dimensional systems. Once these effects are properly removed, we demonstrate that the fast dynamics and slow relaxation comply, without any adjustment, with same scaling between the structural relaxation time and the Debye-Waller factor, originally observed in three-dimensions (3D).

Study of the ground multiplet of Kramers rare earth ions in solid matrices by multifrequency electron paramagnetic resonance spectroscopy: Nd3+ in PbWO4 single-crystals.

A multifrequency electron paramagnetic resonance (EPR) investigation of Nd(3+) impurities in PbWO(4) single-crystals at the conventional microwave frequency (MF) 9.43 GHz, and at the 95, 190, and 285 GHz high frequencies was carried out. The resulting spectra are well described at all frequencies by an axial spin-Hamiltonian corresponding to an effective electron spin of one-half and to a tetragonal symmetry. For the magnetic field along the tetragonal axis, the g(parallel)-factor and the hyperfine constant A(parallel) of the lowest doublet of the ground multiplet decreases with frequency increase. For the magnetic field perpendicular to the tetragonal axis, the g(perpendicular)-factor exhibits a small azimuthal angular dependence that increases with increasing the frequency due to the S(4) site symmetry. The azimuthal angular dependence allows to clearly distinguish between different local axial symmetries. These properties are interpreted as high field/frequency (HF) effects associated with the mixing by the large Zeeman interaction of some of the upper-lying doublets of the ground multiplet into the lowest-lying doublet states. We show that from the combined analysis of the multifrequency MF- and HF-EPR spectra and of the optical data, an accurate description of the ground multiplet of the Kramers rare earth ions in solid matrices can be derived.

Anomaly of the rotational nonergodicity parameter of glass formers probed by high field electron paramagnetic resonance.

Exploiting the high angular resolution of high field electron paramagnetic resonance measured at 95, 190, and 285 GHz we determine the rotational nonergodicity parameter of different probe molecules in the glass former o-terphenyl and polybutadiene in a model-independent way. Our results clearly show a characteristic change in the temperature of the nonergodicity parameter proving a rather sharp dynamic crossover in both systems, in contrast to previous results from other techniques.

Signatures of the fast dynamics in glassy polystyrene: first evidence by high-field electron paramagnetic resonance of molecular guests.

The reorientation of one small paramagnetic molecule (spin probe) in glassy polystyrene (PS) is studied by high-field electron paramagnetic resonance spectroscopy at two different Larmor frequencies (190 and 285 GHz). Two different regimes separated by a crossover region are evidenced. Below 180 K the rotational times are nearly temperature independent with no apparent distribution. In the temperature range of 180-220 K a large increase of the rotational mobility is observed with the widening of the distribution of correlation times which exhibits two components: (i) a deltalike, temperature-independent component representing the fraction of spin probes w which persist in the low-temperature dynamics; (ii) a strongly temperature-dependent component, to be described by a power distribution, representing the fraction of spin probes 1-w undergoing activated motion over an exponential distribution of barrier heights g(E). Above 180 K a steep decrease of w is evidenced. The shape and the width of g(E) do not differ from the reported ones for PS within the errors. For the first time the large increase of the rotational mobility of the spin probe at 180 K is ascribed to the onset of the fast dynamics detected by neutron scattering at T(f)=175+/-25 K.

Delocalization of spin projection in weak exchange linear chains, evidenced by multi-frequency HF-EPR spectroscopy.

High-field electron paramagnetic resonance (HF-EPR) spectroscopy was used to investigate the unusual temperature and frequency dependence of the powder spectrum of the Gd(HBPz3)2 tropolonate complex (GdTrp). A new type of H/T effect is evidenced. This effect is interpreted in terms of the formation of spin projection states delocalized and quasidelocalized along linear chains of Gd3+ ions in high magnetic fields due to the competition between the weak dipole and exchange spin-spin interaction and the particular structure of the molecular complex. The number of ions in the chain depends strongly on the orientation of the magnetic field and on the relaxation processes.

High-field, multifrequency EPR spectroscopy using whispering gallery dielectric resonators.

High-field/high frequency EPR spectroscopy measurements are shown. Experiments were carried out at 240- and 316-GHz frequencies. The employed apparatus uses a novel combination of far infrared molecular lasers and of probehead exploiting dielectric resonators working in the whispering gallery modes. This approach constitutes a relatively simple method of multifrequency EPR spectroscopy and opens appealing perspectives in high-sensitivity EPR spectroscopy up to the THz regime.

Spontaneous symmetry breaking in the formation of a dinuclear gadolinium semiquinonato complex: synthesis, high-field EPR studies, and magnetic properties.

The synthesis and characterisation of an asymmetric dinuclear gadolinium(III) semiquinonato complex, namely [Gd2(HBPz3)2(dtbsq)4] CHCl3 (1; HBPz3 = hydrotris(pyrazolyl)borate, dtbsq = 3,5-di-tert-butyl-O-semiquinone), is reported. The crystal structure of 1 was determined at room temperature. It crystallises in the triclinic system P1, with a = 16.735(5) A, b = 17.705(5) A, c = 19.553(5) A, alpha = 99.680(5) degrees, beta = 109.960(5), gamma = 107.350(5) degrees, Z = 2 and R = 9.96. The structure of 1 consists of a dinuclear asymmetric unit in which the two gadolinium(III) ions have coordination numbers of eight and nine. Three of the dioxolene molecules act as asymmetric bridging ligands, while the fourth molecule behaves as a bidentate ligand towards a single metal ion. The magnetic properties of 1 were investigated by means of susceptibility measurements and high-field electron paramagnetic resonance (HF-EPR) spectroscopy. They revealed an S = 0 ground spin state with excited states of higher spin very close in energy and a small negative zero-field splitting with a transverse anisotropy term for a S = 7 state.