arXiv subjects

Miriam Pena-Alvarez

Publications and source records attributed to Miriam Pena-Alvarez.

5 recordsLinked to original sources

arXiv2026

Theory-Guided Discovery of Pressure-Induced Transitions in Fast-Ion Conductor BaSnF4

Fast-ion conductors such as BaSnF4 are of significant interest for next-generation solid-state battery technologies due to their high ionic conductivity and chemical stability. However, the behaviour of these materials under extreme conditions remains poorly understood, despite the relevance of pressure-induced modifications for tuning functional properties. In this study, we combine density functional theory (DFT) calculations with high-pressure experiments to investigate the structural evolution of BaSnF4 up to 40 GPa. DFT predicts two pressure-induced phase transitions: from the ambient-pressure tetragonal P4/nmm phase to a monoclinic P21/m-I structure at 10 GPa, and subsequently to a denser monoclinic P21/m-II phase at 32 GPa. The first transition is experimentally confirmed via angle-dispersive X-ray diffraction, Raman spectroscopy, and electrical resistivity measurements, all performed at ambient temperature. The second transition is supported by distinct changes in high-pressure Raman modes and resistivity behaviour, consistent with a further structural reorganization. These findings not only clarify the high-pressure phase diagram of BaSnF4, but also shed light on the potential for pressure-tuned ionic transport in fluorostannate-based solid electrolytes.

cond-mat.mtrl-sci↗

arXiv2020

Nuclear Spin Crossover in Dense Molecular Hydrogen

The laws of quantum mechanics are often tested against the behaviour of the lightest element in the periodic table, hydrogen. One of the most striking properties of molecular hydrogen is the coupling between molecular rotational properties and nuclear spin orientations, giving rise to the spin isomers ortho- and para-hydrogen. At high pressure, as intermolecular interactions increase significantly, the free rotation of H2 molecules is increasingly hindered, and consequently a modification of the coupling between molecular rotational properties and the nuclear spin system can be anticipated. To date, high-pressure experimental methods have not been able to observe nuclear spin states at pressures approaching 100 GPa and consequently the effect of high pressure on the nuclear spin statistics could not be directly measured. Here, we present in-situ high-pressure nuclear magnetic resonance data on molecular hydrogen in its hexagonal phase I up to 123 GPa at room temperature. While our measurements confirm the presence of I=1 ortho-hydrogen at low pressures, above 70 GPa, where inter- and intramolecular distances become comparable, we observe a crossover in the nuclear spin statistics from a spin-1 quadrupolar to a spin-1/2 dipolar system, evidencing the loss of spin isomer distinction. These observations represent a unique case of a nuclear spin crossover phenomenon in quantum solids.

cond-mat.mtrl-sci↗

arXiv2019

The Observed Vibron Shift in Helium-Hydrogen Mixtures are due to Quantum Nuclear and Localisation Effects, not bonding

The vibrational frequency of hydrogen molecules has been observed to increase strongly with He concentration in helium hydrogen fluid mixtures. This has been associated with He-H interactions, either directly through chemical bonding, or indirectly through increased local pressure. Here, we demonstrate that the increase in the Raman frequency of the hydrogen molecule vibron is due to the number of H$_2$ molecules participating in the mode. There is no chemical bonding between He and H$_2$, helium acts only to separate the molecules. The variety of possible environments for H$_2$ gives rise to many Raman active modes, which causes broadening the vibron band. As the Raman active modes tend to be the lower frequency vibrons, these effects work together to produce the majority of the shift seen in experiment. We used Density Functional Theory (DFT) methods in both solid and fluid phases to demonstrate this effect. DFT also reveals that the pressure in these H$_2$-He mixture is primarily due to quantum nuclear effects, again the weak chemical bonding makes it a secondary effect.

cond-mat.mtrl-sci↗

arXiv2018

On the Reactivity of Hydrogen-Helium and Hydrogen-Nitrogen at High Pressures

Through a series of Raman spectroscopy studies, we investigate the behaviour of hydrogen-helium and hydrogen-nitrogen mixtures at high pressure across wide ranging concentrations. We find that there is no evidence of chemical association, miscibility, nor any demixing of hydrogen and helium in the solid state up to pressures of 250 GPa at 300 K. In contrast, we observe the formation of concentration-dependent N$_2$-H$_2$ van der Waals solids, which react to form N-H bonded compounds above 50 GPa. Through this combined study, we can demonstrate that the recently claimed chemical association of H$_2$-He can be attributed to significant N$_2$ contamination and subsequent formation of N$_2$-H$_2$ compounds.

cond-mat.mtrl-sci↗

arXiv2018

Graphene under direct compression: stress effects and interlayer coupling

In this work we explore mechanical properties of graphene samples of variable thickness. For this purpose, we coupled a high pressure sapphire anvil cell to a micro-Raman spectrometer. From the evolution of the G band frequency with stress we document the importance the substrate has on the mechanical response of graphene. On the other hand, the appearance of disorder as a conse-quence of the stress treatment has a negligible effect on the high stress behaviour of graphene.

cond-mat.mtrl-sci↗