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We explore the concept of negative pressure and its relevance in a variety of physical contexts: the expansion of the universe, mixture theory, cavitation, and the capillary effect in plants. Using thermodynamic arguments, we discuss the intricate connection between negative pressure and negative thermal expansion. We highlight the fact that metastable states and competing phases are often associated with the emergence of negative pressure. We also propose a new link between the effective Gr\"uneisen parameter and nucleation theory., Comment: 15 pages, 5 figs, comments are welcome

In condensed matter Physics, massive longitudinal Higgs modes emerge from fluctuations of the order parameter. A few years ago, the Higgs mode was \emph{caught} experimentally in the vicinity of an insulator-to-superconductor quantum phase transition [Nat. Phys. $\textbf{11}$, 188 (2015)]. Here, we propose, in analogy to the Higgs mode, the concept of Higgs-like stiffness (HLS), which emerges close to both classical and quantum phase transitions as a universal manifestation of matter. We build up a Landau free energy for the dielectric response function to demonstrate that \emph{any} complex physical quantity can be used to infer the presence of the HLS. Our analysis is corroborated by experimental results of the quasi-static dielectric constant for the (TMTTF)$_2$SbF$_6$ Fabre salt. Yet, we discuss the appearance of fractons in connection with the locking of particular molecular rotational degrees of freedom., Comment: 8 pages, 2 figures. Comments are welcome

Protein compartmentalization in the frame of a liquid-liquid phase separation is a key mechanism to optimize spatiotemporal control of biological systems. Such a compartmentalization process reduces the intrinsic noise in protein concentration due to stochasticity in gene expression. Employing Flory-Huggins solution theory, Avramov/Casalini's model, and the Gr\"uneisen parameter, we unprecedentedly propose a cellular Griffiths-like phase (CGLP), which can impact its functionality and self-organization. The here-proposed CGLP is key ranging from the understanding of primary organisms' evolution to the treatment of diseases. Our findings pave the way for an alternative Biophysics approach to investigate coacervation processes., Comment: 13 pages, 2 figures, suppl. material upon request

For a perfect fluid, pressure $p$ and energy density $\rho$ are related via the equation of state (EOS) $\omega = p/\rho$, where $\omega$ is the EOS parameter, being its interpretation usually constrained to a numerical value for each universe era. Here, based on the Mie-Gr\"uneisen EOS, we show that $\omega$ is recognized as the effective Gr\"uneisen parameter $\Gamma_{eff}$, whose singular contribution, the so-called Gr\"uneisen ratio $\Gamma$, quantifies the barocaloric effect. Our analysis suggests that the negative $p$ associated with dark-energy implies a metastable state and that in the dark-energy-dominated era $\omega$ is time-dependent, which reinforces recent proposals of a time-dependent cosmological constant. Furthermore, we demonstrate that $\Gamma_{eff}$ is embodied in the energy-momentum stress tensor in the Einstein field equations, enabling us to analyse, in the frame of an imperfect fluid picture, anisotropic effects of the universe expansion. We propose that upon going from decelerated- to accelerated-expansion, a phase transition-like behavior can be inferred. Yet, our analysis in terms of entropy, $\Gamma$, and a by us adapted version of Avramov/Casalini's model to Cosmology unveil hidden aspects related to the expansion of the universe. Our findings pave the way to interpret cosmological phenomena in connection with concepts of condensed matter Physics via $\Gamma_{eff}$., Comment: 11 pages, 1 figure, comments are welcome

According to Boltzmann-Gibbs (BG) statistical mechanics, the thermodynamic response, such as the isothermal susceptibility, at critical points (CPs) presents a divergent-like behavior. An appropriate parameter to probe both classical and quantum CPs is the so-called Gr\"uneisen ratio $\Gamma$. Motivated by the results reported in Phys. Rev. B $\textbf{108}$, L140403 (2023), we extend the quantum version of $\Gamma$ to the non-additive $q$-entropy $S_q$. Our findings indicate that using $S_q$ at the unique value of $q$ restoring the extensivity of the entropy, $\Gamma$ is universally non-diverging at CPs. We unprecedentedly introduce $\Gamma$ in terms of $S_q$, being BG recovered for $q \rightarrow 1$. We thus solve a long-standing problem related to the $\textit{illusory}$ diverging susceptibilities at CPs., Comment: 5 pages, 3 figs, comments are welcome

The Gr\"uneisen ratio $\Gamma$, i.e., the singular part of the ratio of thermal expansion to the specific heat, has been broadly employed to explore both finite-$T$ and quantum critical points (QCPs). For a genuine quantum phase transition (QPT), thermal fluctuations are absent and thus the thermodynamic $\Gamma$ cannot be employed. We propose a quantum analogue to $\Gamma$ that computes entanglement as a function of a tuning parameter $\lambda$ and show that QPTs take place only for systems in which the ground-state energy depends on $\lambda$ non-linearly. Furthermore, we demonstrate the breakdown of the Hellmann-Feynman theorem in the thermodynamic limit at any QCP. We showcase our approach using the quantum 1D Ising model with transverse field and Kane's quantum computer. The slowing down of the dynamics and thus the "creation of mass" close to any QCP/QPT is also discussed., Comment: 5 pages, 3 figures, comments are wellcome!

The electrocaloric effect (ECE), i.e., the reversible temperature change due to the adiabatic variation of the electric field, is of great interest due to its potential technological applications. Based on entropy arguments, we present a new framework to attain giant ECE. Our findings are fourfold: $i$) we employ the recently-proposed electric Gr\"uneisen parameter $\Gamma_E$ to quantify the ECE and discuss its advantages over the existing so-called electrocaloric strength; $ii$) prediction of giant caloric effects $close$ to $any$ critical end point; $iii$) proposal of potential key-ingredients to enhance the ECE; $iv$) demonstration of $\Gamma_E$ as a proper parameter to probe quantum ferroelectricity in connection with the celebrated Barrett's formula. Our findings enable us to interpret the recently-reported large ECE at room-temperature in oxide multilayer capacitors [Nature 575, 468 (2019)], paving thus the way for new venues in the field., Comment: 21 pages, 3 figures, 1 table

In real paramagnets, there is always a subtle many-body contribution to the system's energy, which can be regarded as a small effective local magnetic field $B_{loc}$. Usually, it is neglected, since it is very small when compared with thermal fluctuations and/or external magnetic fields $B$. Nevertheless, as both the temperature $T \rightarrow$ 0K and $B \rightarrow$ 0T, such many-body contributions become ubiquitous. Here, employing the magnetic Gr\"uneisen parameter $\Gamma_{mag}$ and entropy arguments, we report on the pivotal role played by the mutual interactions in the regime of ultra-low-$T$ and vanishing $B$. Our key results are: $i$) absence of a genuine zero-field quantum phase transition due to the presence of $B_{loc}$; $ii$) connection between the canonical definition of temperature and $\Gamma_{mag}$; and $iii$) possibility of performing adiabatic magnetization by only manipulating the mutual interactions. Our findings unveil unprecedented aspects emerging from the mutual interactions., Comment: 21 pages, 8 figures

The magneto-caloric effect (MCE), which is the refrigeration based on the variation of the magnetic entropy, is of great interest in both technological applications and fundamental research. The MCE is quantified by the magnetic Gr\"uneisen parameter $\Gamma_{\textmd{mag}}$. We report on an analysis of $\Gamma_{\textmd{mag}}$ for the classical Brillouin-like paramagnet, for a modified Brillouin function taking into account a zero-field splitting originated from the spin-orbit (SO) interaction and for the one-dimensional Ising (1DI) model under longitudinal field. For both Brillouin-like model with SO interaction and the longitudinal 1DI model, for $ T \rightarrow$ 0 and vanishing field a sign change of the MCE is observed, suggestive of a quantum phase transition. SO interaction leads to a narrowing of the critical fluctuations upon approaching the critical point. Our findings emphasize the relevance of $\Gamma_{\textmd{mag}}$ for exploring critical points. Also, we show that the Brillouin model with and without SO interaction can be recovered from the 1DI model in the regime of high-temperatures and vanishing coupling constant $J$., Comment: 10 pages, 12 figures, comments are welcome

We use the recently-proposed \emph{compressible cell} Ising-like model [Phys. Rev. Lett. \textbf{120}, 120603 (2018)] to estimate the ratio between thermal expansivity and specific heat (the Gr\"uneisen parameter $\Gamma$) in supercooled water. Near the critical pressure and temperature, $\Gamma$ increases. The $\Gamma$ value diverges near the pressure-induced finite-$T$ critical end-point [Phys. Rev. Lett. \textbf{104}, 245701 (2010)] and quantum critical points [Phys. Rev. Lett. \textbf{91}, 066404 (2003)], which indicates that two energy scales are governing the system. This enhanced behavior of $\Gamma$ is caused by the coexistence of high- and low-density liquids [Science \textbf{358}, 1543 (2017)]. Our findings support the proposed liquid-liquid critical point in supercooled water in the No-Man's Land regime, and indicates possible applications of this model to other systems., Comment: 5 pages, 4 figures

In strongly correlated organic materials it has been pointed out that charge-ordering could also achieve electronic ferroelectricity at the same critical temperature $T_{co}$. A prototype of such phenomenon are the quasi-one dimensional (TMTTF)$_2X$ Fabre-salts. However, the stabilization of a long-range ferroelectric ground-state below $T_{co}$ requires the break of inversion symmetry, which should be accompanied by a lattice deformation. In this work we investigate the role of the monovalent counter-anion $X$ in such mechanism. For this purpose, we measured the quasi-static dielectric constant along the $c^{*}$-axis direction, where layers formed by donors and anions alternate. Our findings show that the ionic charge contribution is three orders of magnitude lower than the intra-stack electronic response. The $c^{*}$ dielectric constant ($\epsilon'_{c^*}$) probes directly the charge response of the monovalent anion $X$, since the anion mobility in the structure should help to stabilize the ferroelectric ground-state. Furthermore, our $\epsilon'_{c^*}$ measurements %conjugated with earlier investigations of the $c^*$ lattice thermal expansion, show that the dielectric response is thermally broaden below $T_{co}$ if the ferroelectric transition occurs in the temperature range where the anion movement begin to freeze in their methyl groups cavity. In the extreme case of the PF$_6$-H$_{12}$ salt, where $T_{co}$ occurs at the freezing point, a relaxor-type ferroelectricity is observed. Also, because of the slow kinetics of the anion sub-lattice, global hysteresis effects and reduction of the charge response upon successive cycling are observed. In this context, we propose that anions control the order-disorder or relaxation character of the ferroelectric transition of the Fabre-salts., Comment: 8 pages, 7 figures. To appear in Physical Review B

The quasi-two-dimensional organic charge-transfer salt $\kappa$-(BEDT-TTF)$_2$Cu$_2$(CN)$_3$ is one of the prime candidates for a quantum spin-liquid due the strong spin frustration of its anisotropic triangular lattice in combination with its proximity to the Mott transition. Despite intensive investigations of the material's low-temperature properties, several important questions remain to be answered. Particularly puzzling are the 6\,K anomaly and the enigmatic effects observed in magnetic fields. Here we report on low-temperature measurements of lattice effects which were shown to be particularly strongly pronounced in this material (R. S. Manna \emph{et al.}, Phys. Rev. Lett. \textbf{104}, 016403 (2010)). A special focus of our study lies on sample-to-sample variations of these effects and their implications on the interpretation of experimental data. By investigating overall nine single crystals from two different batches, we can state that there are considerable differences in the size of the second-order phase transition anomaly around 6\,K, varying within a factor of 3. In addition, we find field-induced anomalies giving rise to pronounced features in the sample length for two out of these nine crystals for temperatures $T <$ 9 K. We tentatively assign the latter effects to $B$-induced magnetic clusters suspected to nucleate around crystal imperfections. These $B$-induced effects are absent for the crystals where the 6\,K anomaly is most strongly pronounced. The large lattice effects observed at 6\,K are consistent with proposed pairing instabilities of fermionic excitations breaking the lattice symmetry. The strong sample-to-sample variation in the size of the phase transition anomaly suggests that the conversion of the fermions to bosons at the instability is only partial and to some extent influenced by not yet identified sample-specific parameters.

The Gr\"uneisen ratio ($\Gamma$), i.e.\,the ratio of the linear thermal expansivity to the specific heat at constant pressure, quantifies the degree of anharmonicity of the potential governing the physical properties of a system. While $\Gamma$ has been intensively explored in solid state physics, very little is known about its behavior for gases. This is most likely due to the difficulties posed to carry out both thermal expansion and specific heat measurements in gases with high accuracy as a function of pressure and temperature. Furthermore, to the best of our knowledge a comprehensive discussion about the peculiarities of the Gr\"uneisen ratio is still lacking in the literature. Here we report on a detailed and comprehensive overview of the Gr\"uneisen ratio. Particular emphasis is placed on the analysis of $\Gamma$ for gases. The main findings of this work are: \emph{i)} for the Van der Waals gas $\Gamma$ depends only on the co-volume $b$ due to interaction effects, it is smaller than that for the ideal gas ($\Gamma$ = 2/3) and diverges upon approaching the critical volume; \emph{ii)} for the Bose-Einstein condensation of an ideal boson gas, assuming the transition as first-order $\Gamma$ diverges upon approaching a critical volume, similarly to the Van der Waals gas; \emph{iii)} for $^4$He at the superfluid transition $\Gamma$ shows a singular behavior. Our results reveal that $\Gamma$ can be used as an appropriate experimental tool to explore pressure-induced critical points., Comment: 9 pages, 5 figures, comments are wellcome

Specific heat measurements constitute one of the most powerful experimental methods to probe fundamental excitations in solids. After the proposition of Einstein's model, more than one century ago (Annalen der Physik \textbf{22}, 180 (1907)), several theoretical models have been proposed to describe experimental results. Here we report on a detailed analysis of the two-peak specific heat anomalies observed in several materials. Employing a simple multilevel model, varying the spacing between the energy levels $\Delta_i$ = $(E_i$ $-$ $E_{0})$ and the degeneracy of each energy level $g_i$, we derive the required conditions for the appearance of such anomalies. Our findings indicate that a ratio of $\Delta_2$/$\Delta_1$ $\thickapprox$ 10 between the energy levels and a high degeneracy of one of the energy levels define the two-peaks regime in the specific heat. Our approach accurately matches recent experimental results. Furthermore, using a mean-field approach we calculate the specific heat of a degenerate Schottky-like system undergoing a ferromagnetic (FM) phase transition. Our results reveal that as the degeneracy is increased the Schottky maximum in the specific heat becomes narrow while the peak associated with the FM transition remains unaffected., Comment: 7 pages, 5 figures, 33 references

In the field of interacting electron systems the Mott metal-to-insulator (MI) transition represents one of the pivotal issues. The role played by lattice degrees of freedom for the Mott MI transition and the Mott criticality in a variety of materials are current topics under debate. In this context, molecular conductors of the $\kappa$-(BEDT-TTF)$_2$X type constitute a class of materials for unraveling several aspects of the Mott physics. In this review, we present a synopsis of literature results with focus on recent expansivity measurements probing the Mott MI transition in this class of materials. Progress in the description of the Mott critical behavior is also addressed., Comment: Topical review, 30 RevTeX pages, 30 figures

The coupling of magnetic and electronic degrees of freedom to the crystal lattice in the ferromagnetic semimetal EuB$_6$, which exhibits a complex ferromagnetic order and a colossal magnetoresistance (CMR) effect, %, very likely involving magnetic polarons, is studied by high-resolution thermal expansion and magnetostriction experiments. EuB$_6$ may be viewed as a model system, where pure magnetism-tuned transport and the response of the crystal lattice can be studied in a comparatively simple environment,i.e., not influenced by strong crystal-electric field effects and Jahn-Teller distortions. We find a very large lattice response, quantified by (i) the magnetic Gr\"uneisen parameter, (ii) the spontaneous strain when entering the ferromagnetic region and (iii) the magnetostriction in the paramagnetic temperature regime. Our analysis reveals that a significant part of the lattice effects originates in the magnetically-driven delocalization of charge carriers, consistent with the scenario of percolating magnetic polarons. A strong effect of the formation and dynamics of local magnetic clusters on the lattice parameters is suggested to be a general feature of CMR materials., Comment: 5 pages and 3 figures

We present results of ultrasonic measurements on a single crystal of the distorted diamond-chain compound azurite Cu$_3$(CO$_3$)$_2$(OH)$_2$. Pronounced elastic anomalies are observed in the temperature dependence of the longitudinal elastic mode $c_{22}$ which can be assigned to the relevant magnetic interactions in the system and their couplings to the lattice degrees of freedom. From a quantitative analysis of the magnetic contribution to $c_{22}$ the magneto-elastic coupling $G$ = $\partial J_2$/$\partial \epsilon_b$ can be determined, where $J_2$ is the intra-dimer coupling constant and $\epsilon_b$ the strain along the intra-chain $b$ axis. We find an exceptionally large coupling constant of $|G| \sim ($3650 $\pm$ 150) K highlighting an extraordinarily strong sensitivity of $J_2$ against changes of the $b$-axis lattice parameter. These results are complemented by measurements of the hydrostatic pressure dependence of $J_2$ by means of thermal expansion and magnetic susceptibility measurements performed both at ambient and finite hydrostatic pressure. We propose that a structural peculiarity of this compound, in which Cu$_2$O$_6$ dimer units are incorporated in an unusually stretched manner, is responsible for the anomalously large magneto-elastic coupling., Comment: 9 pages, 6 figures

The organic charge-transfer salt EtMe$_3$P[Pd(dmit)$_2$]$_2$ is a quasi-two-dimensional Mott insulator with localized spins $S$ = 1/2 residing on a distorted triangular lattice. Here we report measurements of the uniaxial thermal expansion coefficients $\alpha_i$ along the in-plane $i$ = $a$- and $c$-axis as well as along the out-of-plane $b$-axis for temperatures 1.4\,K $\leq $T$ \leq$ 200\,K. Particular attention is paid to the lattice effects around the phase transition at $T_{VBS}$ = 25\,K into a low-temperature valence-bond-solid phase and the paramagnetic regime above where effects of short-range antiferromagnetic correlations can be expected. The salient results of our study include (i) the observation of strongly anisotropic lattice distortions accompanying the formation of the valence-bond-solid, and (ii) a distinct maximum in the thermal expansion coefficients in the paramagnetic regime around 40\,K. Our results demonstrate that upon cooling through $T_{VBS}$ the in-plane $c$-axis, along which the valence bonds form, contracts while the second in-plane $a$-axis elongates by the same relative amount. Surprisingly, the dominant effect is observed for the out-of-plane $b$-axis which shrinks significantly upon cooling through $T_{VBS}$. The pronounced anomaly in $\alpha_i$ around 40\,K is attributed to short-range magnetic correlations. It is argued that the position of this maximum, relative to that in the magnetic susceptibility around 70\,K, speaks in favor of a more anisotropic triangular-lattice scenario for this compound than previously thought., Comment: 6 pages, 4 figures, submitted to Phys. Rev. B

Charge-ordering phenomena have been highly topical over the last few years. A phase transition towards a charge ordered state has been observed experimentally in several classes of materials. Among them, many studies have been devoted to the family of quasi-one dimensional organic charge-transfer salts (TMTTF)$_2$X, where (TMTTF) stands for tetramethyltetrathiafulvalene and X for a monovalent anion (X = PF$_6$, AsF$_6$ and SbF$_6$). However, the relationship between the electron localization phenomena and the role of the lattice distortion in stabilizing the charge-ordering pattern is poorly documented in the literature. Here we present a brief overview of selected literature results with emphasis placed on recent thermal expansion experiments probing the charge-ordering transition of these salts., Comment: 21 pages, 17 figures

We present ultra-high-resolution dilatometric studies in magnetic fields on a quasi-two-dimensional organic conductor $\kappa$-(D8-BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Br, which is located close to the Mott metal-insulator (MI) transition. The obtained thermal expansion coefficient, $\alpha(T)$, reveals two remarkable features: (i) the Mott MI transition temperature $T_{MI}$ = (13.6 $\pm$ 0.6)\,K is insensitive to fields up to 10\,T, the highest applied field; (ii) for fields along the interlayer \emph{b}-axis, a magnetic-field-induced (FI) phase transition at $T_{FI}$ = (9.5 $\pm$ 0.5)\,K is observed above a threshold field $H_c \sim$ 1 T, indicative of a spin reorientation with strong magneto-elastic coupling., Comment: 5 pages, 4 figures

Measurements of the coefficient of thermal expansion on the spin-liquid candidate $\kappa$-(BEDT-TTF)$_2$Cu$_2$(CN)$_3$ have revealed distinct and strongly anisotropic lattice effects around 6 K - a possible spin-liquid instability. In order to study the effects of a magnetic field on the low-temperature spin-liquid state, dilatometric measurements have been conducted both as a function of temperature at \emph{B} = const. and as a function of field at \emph{T} = const. While the 6 K anomaly is found to be insensitive to magnetic fields \emph{B} $\leq$ 10 T, the maximum field applied, surprisingly strong \emph{B}-induced effects are observed for magnetic fields applied along the in-plane \emph{b}-axis. Above a threshold field of 0.5 T < \emph{B}$_c$ $\leq$ 1 T, a jump-like anomaly is observed in the \emph{b}-axis lattice parameter. This anomaly, which is located at 8.7 K at \emph{B} = 1 T, grows in size and shifts to lower temperatures with increasing the magnetic field. Although the anomaly bears resemblance to a first-order phase transition, the lack of hysteresis suggests otherwise., Comment: 3 pages, 3 figures, proceedings of ISCOM 2011, physica status solidi (c)(in press)

We investigate the effect that the temperature dependence of the crystal structure of a two dimensional organic charge-transfer salt has on the low-energy Hamiltonian representation of the electronic structure. For that, we determine the crystal structure of kappa-(BEDT-TTF)2Cu2(CN)3 for a series of temperatures between T=5 K and 300 K by single crystal X-ray diffraction and analyze the evolution of the electronic structure with temperature by using density functional theory and tight binding methods. We find a considerable temperature dependence of the corresponding triangular lattice Hubbard Hamiltonian parameters. We conclude that even in the absence of change of symmetry, the temperature dependence of quantities like frustration and interaction strength can be significant and should be taken into account., Comment: 8 pages, 9 figures

We report on synthesis, structural characterization, resistivity, magnetic and thermal expansion measurements on the as yet unexplored $\delta'$-phase of FeSe$_{1-x}$, here synthesized under ambient- (AP) and high-pressure (HP) conditions. We show that in contrast to $\beta$-FeSe$_{1-x}$, monophasic superconducting $\delta'$-FeSe$_{1-x}$ can be obtained in off-stoichiometric samples with excess Fe atoms preferentially residing in the van der Waals gap between the FeSe layers. The AP $\delta'$-FeSe$_{1-x}$ sample studied here ($T_c$ $\simeq$ 8.5\,K) possesses an unprecedented residual resistivity ratio RRR $\simeq$ 16. Thermal expansion data reveal a small feature around $\sim$90\,K, which resembles the anomaly observed at the structural and magnetic transitions for other Fe-based superconductors, suggesting that some kind of "magnetic state" is formed also in FeSe. %indicative of a fluctuating magnetic ordering. For HP samples (RRR $\simeq$ 3), the disorder within the FeSe layers is enhanced through the introduction of vacancies, the saturated magnetic moment of Fe is reduced and only spurious superconductivity is observed., Comment: 7 pages, 8 figures, published version

We discuss a scaling theory of the lattice response in the vicinity of a finite-temperature critical end point. The thermal expansivity is shown to be more singular than the specific heat such that the Gr\"uneisen ratio diverges as the critical point is approached, except for its immediate vicinity. More generally, we express the thermal expansivity in terms of a scaling function which we explicitly evaluate for the two-dimensional Ising universality class. Recent thermal expansivity measurements on the layered organic conductor kappa-(BEDT-TTF)_2 X close to the Mott transition are well described by our theory., Comment: 4 REVTeX pages, 4 figures; minor changes, as published

We report results of high-resolution measurements of the \emph{c$^*$}-axis expansivity ($\alpha_{c^{*}}$) at the charge-ordering (CO) transition for the quasi-1D (TMTTF)$_{2}$X compounds with X = SbF$_6$ and Br and make a comparison with previous results for the X = PF$_6$ and AsF$_6$ salts. For X = SbF$_6$, due to the screening of the long-range Coulomb forces, a sharp $\lambda$-type anomaly is observed at $T_{CO}$, which contrasts with the step-like mean-field anomaly at $T_{CO}$ for PF$_6$ and AsF$_6$, where CO occurs in the Mott-Hubbard charge-localized regime. For the latter two salts, a negative contribution to $\alpha_{c^{*}}$ is observed above $T_{CO}$. This feature is assigned to the anions' rigid-unit modes, which become inactive for $T$ $<$ $T_{CO}$. Our $\alpha_{c^{*}}$ results for the X = Br salt, where such rigid-unit modes are absent, reveal no traces of such negative contribution, confirming the model based on the anions' rigid-unit modes for the X = PF$_6$ and AsF$_6$ salts., Comment: Submitted to Special Issue - ISCOM 2009 - Physica B Condensed Matter