Heat capacity of the quantum magnet TiOCl

Measurements of the heat capacity C(T,H) of the one-dimensional quantum magnet TiOCl are presented for temperatures 2K < T < 300K and magnetic fields up to 5T. Distinct anomalies at 91K and 67K signal two subsequent phase transitions. The lower of these transitions clearly is of first order and seems to be related to the spin degrees of freedom. The transition at 92K probably involves the lattice and/or orbital moments. A detailed analysis of the data reveals that the entropy change through both transitions is surprisingly small (~ 0.1R), pointing to the existence strong fluctuations well into the non-ordered high-temperature phase. No significant magnetic field dependence was detected.Comment: 4 pages, 2 figure

Spin-Peierls transition in TiOCl

Temperature-dependent x-ray diffraction of the low-dimensional spin 1/2 quantum magnet TiOCl shows that the phase transition at T_{c2} = 90 K corresponds to a lowering of the lattice symmetry. Below T_{c1} = 66 K a twofold superstructure develops, that indicates the formation of spin-singlet pairs via direct exchange between neighboring Ti atoms, while the role of superexchange is found to be negligible. TiOCl thus is identified as a spin-Peierls system of pure 1D chains of atoms. The first-order character of the transition at T_{c1} is explained by the competition between the structurally deformed state below T_{c2} and the spin-Peierls state below T_{c1}.Comment: Phys. Rev. B (Rapid Communications) in pres

Gas adsorption/desorption in silica aerogels: a theoretical study of scattering properties

We present a numerical study of the structural correlations associated to gas adsorption/desorption in silica aerogels in order to provide a theoretical interpretation of scattering experiments. Following our earlier work, we use a coarse-grained lattice-gas description and determine the nonequilibrium behavior of the adsorbed gas within a local mean-field analysis. We focus on the differences between the adsorption and desorption mechanisms and their signature in the fluid-fluid and gel-fluid structure factors as a function of temperature. At low temperature, but still in the regime where the isotherms are continuous, we find that the adsorbed fluid density, during both filling and draining, is correlated over distances that may be much larger than the gel correlation length. In particular, extended fractal correlations may occur during desorption, indicating the existence of a ramified cluster of vapor filled cavities. This also induces an important increase of the scattering intensity at small wave vectors. The similarity and differences with the scattering of fluids in other porous solids such as Vycor are discussed.Comment: 16 pages, 15 figure

Pressure-induced insulator-to-metal transition in low-dimensional TiOCl

We studied the transmittance and reflectance of the low-dimensional Mott-Hubbard insulator TiOCl in the infrared and visible frequency range as a function of pressure. The strong suppression of the transmittance and the abrupt increase of the near-infrared reflectance above 12 GPa suggest a pressure-induced insulator-to-metal transition. The pressure-dependent frequency shifts of the orbital excitations, as well as the pressure dependences of the charge gap and the spectral weight of the optical conductivity above the phase transition are presented.Comment: 4 pages, 6 figure

Muon-spin relaxation measurements on the dimerized spin-1/2 chains NaTiSi2O6 and TiOCl

We report muon spin relaxation (muSR) and magnetic susceptibility investigations of two Ti3+ chain compounds which each exhibit a spin gap at low temperature, NaTiSi2O6 and TiOCl. From these we conclude that the spin gap in NaTiSi2O6 is temperature independent, with a value of 2*Delta=660(50)K, arising from orbital ordering at Too = 210K; the associated structural fluctuations activate the muon spin relaxation rate up to temperatures above 270K. In TiOCl we find thermally activated spin fluctuations corresponding to a spin gap 2*Delta=420(40)K below Tc1=67K. We also compare the methods used to extract the spin gap and the concentration of free spins within the samples from muSR and magnetic susceptibility data.Comment: 4 pages, 3 figure

Are the renormalized band widths in TTF-TCNQ of structural or electronic origin? - An angular dependent NEXAFS study

We have performed angle-dependent near-edge x-ray absorption fine structure measurements in the Auger electron yield mode on the correlated quasi-one-dimensional organic conductor TTF-TCNQ in order to determine the orientation of the molecules in the topmost surface layer. We find that the tilt angles of the molecules with respect to the one-dimensional axis are essentially the same as in the bulk. Thus we can rule out surface relaxation as the origin of the renormalized band widths which were inferred from the analysis of photoemission data within the one-dimensional Hubbard model. Thereby recent theoretical results are corroborated which invoke long-range Coulomb repulsion as alternative explanation to understand the spectral dispersions of TTF-TCNQ quantitatively within an extended Hubbard model.Comment: 6 pages, 5 figure

Spin dynamics in the low-dimensional magnet TiOCl

We present detailed ESR investigations on single crystals of the low-dimensional quantum magnet TiOCl. The anisotropy of the g-factor indicates a stable orbital configuration below room temperature, and allows to estimate the energy of the first excited state as 0.3(1) eV ruling out a possible degeneracy of the orbital ground state. Moreover, we discuss the possible spin relaxation mechanisms in TiOCl and analyze the angular and temperature dependence of the linewidth up to 250 K in terms of anisotropic exchange interactions. Towards higher temperatures an exponential increase of the linewidth is observed, indicating an additional relaxation mechanism.Comment: 10 pages, 8 figures; accepted for publication in Phys. Rev.