Quantum Dynamics of H-2 and D-2 Confined in Hydrate Structures as a Function of Pressure and Temperature

We present an extensive study of the quantum dynamics of molecular hydrogen trapped within the nanocavities of two hydrate structures at low temperatures, namely, clathrate structure II and filled ice structure Cl. By inelastic neutron scattering measurements, we investigate a (i) simple H-2 hydrate in clathrate structure II at ambient and high pressure and different temperatures, (ii) binary He-H-2 hydrate in clathrate structure II at high pressure and different temperatures, (iii) simple D-2 hydrate in clathrate structure II at ambient pressure and different temperatures, and (iv) simple H-2 hydrate in structure Cl at high pressure and different temperatures. Molecular quantum rotations and translations, as well as combinations of these are identified in the spectra for hydrogen molecules in the small and large cages of clathrate structure II and in the channels of structure Cl and their energy is provided.

Translational and Rotational Diffusion in Water in the Gigapascal Range

Livia Eleonora Bove Kado

First measurements of the self-dynamics of liquid water in the GPa range are reported. The GPa range has here become accessible through a new setup for the Paris-Edinburgh press specially conceived for quasielastic neutron scattering studies. A direct measurement of both the translational and rotational diffusion coefficients of water along the 400 K isotherm up to 3 GPa, corresponding to the melting point of ice VII, is provided and compared with molecular dynamics simulations. The translational diffusion is observed to strongly decrease with pressure, though its variation slows down for pressures higher than 1 GPa and decouples from that of the shear viscosity. The rotational diffusion turns out to be insensitive to pressure. Through comparison with structural data and molecular dynamics simulations, we show that this is a consequence of the rigidity of the first neighbors shell and of the invariance of the number of hydrogen bonds of a water molecule under high pressure. These results show the inadequacy of the Stokes-Einstein-Debye equations to predict the self-diffusive behavior of water at high temperature and high pressure, and challenge the usual description of hot dense water behaving as a simple liquid.

American Physical Society2013

X‑ray and Neutron Scattering of Water

Livia Eleonora Bove Kado

This review article focuses on the most recent advances in X-ray and neutron scattering studies of water structure, from ambient temperature to the deeply supercooled and amorphous states, and of water diffusive and collective dynamics, in disparate thermodynamic conditions and environments. In particular, the ability to measure X-ray and neutron diffraction of water with unprecedented high accuracy in an extended range of momentum transfers has allowed the derivation of detailed O-O pair correlation functions. A panorama of the diffusive dynamics of water in a wide range of temperatures (from 400 K down to supercooled water) and pressures (from ambient up to multiple gigapascals) is presented. The recent results obtained by quasi-elastic neutron scattering under high pressure are compared with the existing data from nuclear magnetic resonance, dielectric and infrared measurements, and modeling. A detailed description of the vibrational dynamics of water as measured by inelastic neutron scattering is presented. The dependence of the water vibrational density of states on temperature and pressure, and in the presence of biological molecules, is discussed. Results about the collective dynamics of water and its dispersion curves as measured by coherent inelastic neutron scattering and inelastic X-ray scattering in different thermodynamic conditions are reported.

American Chemical Society2016

Normal state transport properties of novel superconductors

Balazs Sipos

The discovery of high temperature superconductivity in the cuprates in 1986 has boosted the research in strongly correlated materials. One strong motivation was and stays the understanding the high-Tc phenomenon with the hope that one can ultimately engineer new materials with even higher Tc. Besides the in-depth investigation of cuprates, there is a strong tendency in the solid state community to find new superconductors, which by themselves are interesting for applications, or by their properties they can contribute to the understanding of the high-Tc phenomenon. The program of my doctoral thesis was three-fold: i) to address one important issue in the cuprate superconductors, that of the role of homogeneity in the underdoped part of the phase diagram; ii) what is the effect of disorder in MgB2 superconductor, which has high potentials for applications; iii) to discover new superconductors in the family of transition metal dichalcogenides. All these materials are in some sense unconventional superconductors. The cuprates by their high Tc and the symmetry of the order parameter, MgB2 by its two-band superconductivity and Tc of 39 K, and the dichalcogenides by the appearance of superconductivity on the background of competing interactions. Measurements of transport properties, such as resistivity and thermoelectric power, were used to get insight in the behavior of these materials. Besides temperature as variable, I applied high pressure, extreme magnetic fields and controlled disorder introduced by fast electron irradiation. In the first part I present the pressure dependent study of two members of the transition metal dichalcogenides having 1T structure, 1T-TiSe2 and 1T-TaS2, where superconductivity was never observed in a pristine sample. 1T-TiSe2 has a CDW phase below 220 K which origin, weather it is driven by an excitonic mechanism or by a Jahn-Teller distortion, is an ongoing question. By applying pressure I showed that the pristine sample is superconducting in the pressure range of 2.0–4.0 GPa. This range remarkably coincides with the short range fluctuating CDW before its disappearance at the upper pressure value. If CDW is due to excitonic interactions than our observations suggest that it can be at the origin of superconductivity, as well. The second dichalcogenide is the 1T-TaS2, where a Mott-insulator phase appears on the top of a commensurate CDW. By applying pressure I was able to melt that Mott-phase, and reveal that the material is superconducting above 2.5 GPa with Tc of 5.9 K. Unexpectedly, superconductivity is born from a nonmetallic phase, and stays remarkably stable up to the highest applied pressure of 24 GPa. In the second part I tried to give my contribution to the field of high-Tc superconductors. I carefully selected few high quality underdoped Bi2Sr2PrxCa1-xCu2O8-δ sample, to address the nature of the low temperature ground state by applying high magnetic field. Although former measurements by other groups showed that at high underdoping, the ground state is an insulator, I found that a sample with as low Tc as 15 K exhibits metallic behavior up to 60 T. Furthermore, I showed that a inhomogeneous distribution of the doping atoms can completely mask the intrinsic normal state of a high-Tc superconductor. In the last part of my thesis I focused on the two-band superconductor MgB2 by studying the scattering between the bands by the means of the Matthiessen's rule. I made a systematic study of the influence of defects created by fast electron irradiation, and found that the the Matthiessen's rule is satisfied for the defect concentration range I induced. I further compare the influence of defects on the critical temperature and the residual resistivity in MgB2 with superconductors with various order parameters, and found that the decrease-rate of Tc in our system is within the range of a response of a superconductor with an s-wave order parameter.

EPFL2008

Normal state transport properties of novel superconductors

Balazs Sipos

EPFL2008