The Grüneisen parameter applied to critical phenomena and experimental investigations of correlated phenomena in molecular conductors

Abstract

In this Ph.D. Thesis, a systematic review is performed on the derivation and generalization of the Grüneisen parameter followed by its unprecedented applications to several distinct scenarios, such as magnetic model systems, zero-field quantum phase transitions, the maximization of caloric effects close to any critical-end point based on entropy arguments, the here-proposed adiabatic magnetization of a paramagnetic salt, as well as for Cosmology in the frame of the universe expansion. Since this Ph.D. Thesis is a symbiosis between theoretical and experimental results, an experimental investigation of correlated phenomena was carried out for molecular conductors of the (TMTTF)$_2$X family, where TMTTF is the base molecule tetramethyltetrathiafulvalene and X a monovalent counter-anion such as PF$_6$, SbF$_6$, or AsF$_6$. Such strongly correlated electron systems are considered suitable ones for the exploration of Mott insulating phase, charge-ordering, spin-Peierls, and superconductivity. In particular, the investigation of a possible multiferroic character in these salts was performed via quasi-static (low-frequency) dielectric constant $\varepsilon'$ measurements as a function of temperature where a maximum in $\varepsilon'$ as a function of temperature was observed at the corresponding charge-ordering temperature for both hydrogenated and 97.5% deuterated (TMTTF)$_2$SbF$_6$ salts. Furthermore, Raman measurements were performed on the 97.5% deuterated (TMTTF)$_2$PF$_6$, showing a possible magneto-optical effect on the $ν_4(a_g)$ vibrational mode of the TMTTF molecule. Yet, fluorescence measurements demonstrated that the fully-hydrogenated (TMTTF)$_2$AsF$_6$ presents an expressive fluorescence background, which is roughly five orders of magnitude lower than that for the 97.5% deuterated variant of (TMTTF)$_2$PF$_6$.