Evidence for Lattice Effects at the Charge-Ordering Transition in (TMTTF)2_2X

High-resolution thermal expansion measurements have been performed for exploring the mysterious "structureless transition" in (TMTTF)$_{2}$X (X = PF$_{6}$ and AsF$_{6}$), where charge ordering at $T_{CO}$ coincides with the onset of ferroelectric order. Particularly distinct lattice effects are found at $T_{CO}$ in the uniaxial expansivity along the interstack $\textbf{\textit{c*}}$-direction. We propose a scheme involving a charge modulation along the TMTTF stacks and its coupling to displacements of the counteranions X$^{-}$. These anion shifts, which lift the inversion symmetry enabling ferroelectric order to develop, determine the 3D charge pattern without ambiguity. Evidence is found for another anomaly for both materials at $T_{int}$ $\simeq$ 0.6 $\cdot$ $T_{CO}$ indicative of a phase transition related to the charge ordering

Resonant inelastic x-ray scattering probes the electron-phonon coupling in the spin-liquid kappa-(BEDT-TTF)2Cu2(CN)3

Resonant inelastic x-ray scattering at the N K edge reveals clearly resolved harmonics of the anion plane vibrations in the kappa-(BEDT-TTF)2Cu2(CN)3 spin-liquid insulator. Tuning the incoming light energy at the K edge of two distinct N sites permits to excite different sets of phonon modes. Cyanide CN stretching mode is selected at the edge of the ordered N sites which are more strongly connected to the BEDT-TTF molecules, while positionally disordered N sites show multi-mode excitation. Combining measurements with calculations on an anion plane cluster permits to estimate the sitedependent electron-phonon coupling of the modes related to nitrogen excitation

Low temperature structural effects in the (TMTSF)2_2PF6_6 and AsF6_6 Bechgaard salts

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF)$_2$PF$_6$ and (TMTSF)$_2$AsF$_6$ (TMTSF : tetramethyl-tetraselenafulvalene). The 4 K neutron scattering structure refinement of the fully deuterated (TMTSF)$_2$PF$_6$-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)$_2$PF$_6$-H12 salt previously determined at the same temperature. Surprisingly it is found that deuteration corresponds to the application of a negative pressure of 5 x 10$^2$ MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF$_6$ and AsF$_6$ salts. Two different thermal behaviors have been distinguished. Low-Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies {\theta}$_E$ = 8.3 K and {\theta}$_E$ = 6.7 K for the PF$_6$-D12 and AsF$_6$-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large-Bragg-angle measurements evidence an unexpected structural change around 55 K which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)$_2$PF$_6$ is dominated by the librational motion of the PF$_6$ units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: {\theta}$_E$ = 50 K and {\theta}$_E$ = 76 K for the PF$_6$-D12 and PF$_6$-H12 salts, respectively

Purely antiferromagnetic frustrated Heisenberg model in spin ladder compound BaFe2_2Se3_3

The spin dynamics in the block magnetic phase of the iron-based ladder compound \bfs\ has been studied by means of single crystal inelastic neutron scattering. Using linear spin wave theory and Monte-Carlo simulations, our analysis points to a magnetic Heisenberg model with effective frustrated antiferromagnetic couplings only, able to describe both the exotic block order and its dynamics. This new and purely antiferromagnetic picture offers a fruitful perspective to describe multiferroic properties but also understand the origin of the stripe-like magnetic instability observed under pressure as well as in other parent compounds with similar crystalline structure

Ground State of the Quasi-1D \bvs\ resolved by Resonant Magnetic X-ray Scattering

Resonant-magnetic x-ray scattering (RMXS) near the vanadium $L_{2,3}$-absorption edges has been used to investigate the low temperature magnetic structure of high quality \bvs\ single crystals. Below $T_N$ = 31 K, the strong resonance revealed a triple-incommensurate magnetic ordering at wave vector (0.226 0.226 $\xi$) in the hexagonal notation, with $\xi$ = 0.033. The simulations of the experimental RMXS spectra with a time-dependent density functional theory indicate an antiferromagnetic order with the spins polarized along $a$ in the monoclinic structure.Comment: 4 pages, 4 figures, submitted to Phys. Rev. Let

Microwave dielectric study of spin-Peierls and charge ordering transitions in (TMTTF)2_2PF6_6 salts

We report a study of the 16.5 GHz dielectric function of hydrogenated and deuterated organic salts (TMTTF)$_2$PF$_6$. The temperature behavior of the dielectric function is consistent with short-range polar order whose relaxation time decreases rapidly below the charge ordering temperature. If this transition has more a relaxor character in the hydrogenated salt, charge ordering is strengthened in the deuterated one where the transition temperature has increased by more than thirty percent. Anomalies in the dielectric function are also observed in the spin-Peierls ground state revealing some intricate lattice effects in a temperature range where both phases coexist. The variation of the spin-Peierls ordering temperature under magnetic field appears to follow a mean-field prediction despite the presence of spin-Peierls fluctuations over a very wide temperature range in the charge ordered state of these salts.Comment: 7 pages, 6 figure

Charge ordering, symmetry and electronic structure issues and Wigner crystal structure of the quarter-filled band Mott insulators and high pressure metals δ-(EDT-TTF-CONMe2)2X, X = Br and AsF6

We report on the synthesis and application of an internal chemical pressure to effectively control, and reduce, the Mott gap in the system δ-(EDT-TTF-CONMe2)2X, X = Br, AsF6; the detailed accounts of its Pmna, averaged room temperature structure and reversible phase transition at ca. 190 K towards a low tem

Near-Edge X‐ray Absorption Fine Structure Investigation of the Quasi-One-Dimensional Organic Conductor (TMTSF)2PF6

We present high-resolution near-edge X-ray absorption fine structure (NEXAFS) measurements at the P L2/3 edges, F K edge, C K edge, and Se M2/3 edges of the quasi-one-dimensional (1D) conductor and superconductor (TMTSF)2PF6. NEXAFS allows probing the donor and acceptor moieties separately; spectra were recorded between room temperature (RT) and 30 K at normal incidence. Spectra taken around RT were also studied as a function of the angle (θ) between the electric field of the X-ray beam and the 1D conducting direction. In contrast with a previous study of the S L2/3-edges spectra in (TMTTF)2AsF6, the Se M2/3 edges of (TMTSF)2PF6 do not exhibit a well-resolved spectrum. Surprisingly, the C K-edge spectra contain three well-defined peaks exhibiting strong and nontrivial θ and temperature dependence. The nature of these peaks as well as those of the F K-edge spectra could be rationalized on the basis of first-principles DFT calculations. Despite the structural similarity, the NEXAFS spectra of (TMTSF)2PF6 and (TMTTF)2AsF6 exhibit important differences. In contrast with the case of (TMTTF)2AsF6, the F K-edge spectra of (TMTSF)2PF6 do not change with temperature despite stronger donor−anion interactions. All these features reveal subtle differences in the electronic structure of the TMTSF and TMTTF families of salts

A new quantum fluid at high magnetic fields in the marginal charge-density-wave system α\alpha-(BEDT-TTF)2M_2MHg(SCN)4_4 (where M=M=~K and Rb)

Single crystals of the organic charge-transfer salts $\alpha$-(BEDT-TTF)$_2M$Hg(SCN)$_4$ have been studied using Hall-potential measurements ($M=$K) and magnetization experiments ($M$ = K, Rb). The data show that two types of screening currents occur within the high-field, low-temperature CDW$_x$ phases of these salts in response to time-dependent magnetic fields. The first, which gives rise to the induced Hall potential, is a free current (${\bf j}_{\rm free}$), present at the surface of the sample. The time constant for the decay of these currents is much longer than that expected from the sample resistivity. The second component of the current appears to be magnetic (${\bf j}_{\rm mag}$), in that it is a microscopic, quasi-orbital effect; it is evenly distributed within the bulk of the sample upon saturation. To explain these data, we propose a simple model invoking a new type of quantum fluid comprising a CDW coexisting with a two-dimensional Fermi-surface pocket which describes the two types of current. The model and data are able to account for the body of previous experimental data which had generated apparently contradictory interpretations in terms of the quantum Hall effect or superconductivity.Comment: 13 pages, 11 figure