Structural and electrical properties of (BEDT-TTF)(TCNQ)

An organic complex (BEDT-TTF)(TCNQ) (BEDT-TTF: bis(ethylene-dithio) tetrathiafulvalene, TCNQ: tetracyanoquinodimethane) crystallizes in two different phases: the monoclinic phase and the triclinic phase. In the triclinic phase the TCNQ molecules are stacked face to face, whereas the BEDT-TTF molecules are arranged side by side along the TCNQ stacks. This complex undergoes a metal-semiconductor transition a little above room temperature. The measurement of anisotropic thermoelectric power shows that the electron conduction on the TCNQ column is superior to the hole conduction on the BEDT-TTF only along the stacking direction of TCNQ and only above the phase transition. This result is consistent with the tight-binding band structure calculation.     

Low temperature structural phase transition in hafnium and zirconium tetrafluoride trihydrates

From time-differential perturbed angular correlation (TDPAC) measurements, the monoclinic and triclinic crystal structures in hafnium and zirconium tetrafluoride trihydrates are found to be present simultaneously in both the compounds. From previous TDPAC and XRD investigations, a monoclinic crystal structure for HfF₄·3H₂O but, for its analogues zirconium compound, a triclinic structure was reported. Contrary to earlier reports, the triclinic fraction in HfF₄·3H₂O is found to be maximum (80%) at room temperature. In fact, the triclinic crystal structure of HfF₄·3H₂O is reported here which was not known prior to this report. In ZrF₄·3H₂O, a strong signal (80–90%) for the triclinic structure is found at room temperature while the monoclinic fraction appears as a weak signal (10–15%). Structural phase transitions in these trihydrate compounds have been observed in the temperature range 298–333 K.     

X-ray study of the phase transition in RbHSeO4

The ferroelectric phase transition in RbHSeO₄ has been examined by precise measurements of the temperature dependence of the unit-cell parameters using the Bond technique. The transition, at T_c = 370.6 K, is of first order and the triclinic unit cell of the ferroelectric phase transforms to an equitranslational monoclinic cell in the paraelectric phase. In a temperature region of several K below T_c reflections belonging to both phases have been observed.     

Structural and lattice-energy analyses of the different low-temperature phases of ferrocene Fe(C5H5)2: Relation between the molecular packings

X-Ray analysis of the metastable triclinic phase of ferrocene has been carried out at 130 K, from a single crystal cooled through the transition temperature (164 K). The molecular packing is close to a face centred one; however the numerous reflections breaking this symmetry give evidence for a P1 or P1̄ superstructure which appears to be disordered. Calculations of lattice energy performed at 130 K and 15 K show that the triclinic phase of ferrocene has two possible molecular packings, quite energetically similar, of face-centred or P1̄ symmetry. Thus, when the triclinic phase is obtained by cooling a crystal from room temperature, its structure is constituted by a mixture of both packings whose ratio depends on the thermal history. On the other hand, the molecular coordinates and the configuration of ferrocene (D_5h) in the stable ordered orthorhombic phase have been determined by minimizing the lattice energy. The mechanism of the order-disorder phase transition at 250 K (orthorhombic monoclinic), as also the existence below 164 K of another ordered packing, the triclinic one, are discussed in terms of ring libration.     

Observation of quasi-universal magnetic behavior in a random exchange Heisenberg antiferromagnetic chain: Neutron irradiated quinolinium (TCNQ)2

Low field electron spin resonance measurements of the magnetic susceptibility (χ) and absorption linewidth over the temperature range 0.04 – 300 K are reported for quinolinium (TCNQ)₂ into which increased amounts of disorder have been introduced by fast neutron irradiation. It is found that below 20 K, χ = AT^-α; A increases linearly with the irradiation dose, but $\text{α (? 0.8)}$ is almost independent of it, in agreement with the quasi universal behavior predicted by recent renormalization calculations for a random exchange Heisenberg antiferromagnetic chain. Measurements of the g-shift at 4.2 K range indicate that all of χ is associated with TCNQ chains. These results are discussed in terms of the renormalization calculation of Soos and Bondeson.     

Some magnetic properties of Mn(TCNQ)2

The EPR spectra of polycrystalline Mn(TCNQ)₂·3H₂O and Mn(TCNQ?d₄)₂ have been studied as a function of temperature from 1.5 K to 375 K. At very low temperatures the line width indicates an exchange interaction similar to that of other manganese salts. At 77 K and above the line is narrowed and shifted most likely through interaction with the electronic motion. The bulk susceptibility was measured at room temperature. The observed μ_eff=4.66 implies an antiferromagnetic coupling of the manganese ions.     

Static dielectric constant of disordered organic quasi one-dimensional conductors: Localization by defects

We have measured the low temperature dielectric constant ? of two similar quasi one-dimensional organic conductors, N-Me-iso Qn(TCNQ)₂ and Qn(TCNQ)₂. For N-Me-iso Qn(TCNQ)₂ below 10 K, ? is independent of temperature and is frequency independent in the range 5 × 10⁵ Hz to 9 × 10⁹ Hz, within the 50% experimental uncertainty. Thus we believe the low temperature microwave dielectric constant to be a good approximation of the static value in this salt. For Qn(TCNQ)₂ at low temperatures, the relation ? ∝ (c+c₀)^-2 holds, where c is the defect concentration and c₀ is an effective defect concentration of the nominally pure material. This relation is predicted by the model of interrupted metallic strands with energy spacings larger than kT, and it indicates that electrons are strongly localized by defects along the conducting chains.     

Electronic absorption spectrum of Cs<Subscript>2</Subscript>ZnI<Subscript>4</Subscript> thin films

The absorption spectrum of Cs₂ZnI₄ thin films in the energy range 3–6 eV at temperatures from 90 to 340 K has been investigated. It is established that this compound belongs to direct-gap insulators. Low-frequency exciton excitations are localized in ZnI₄ structural elements of the lattice. Phase transitions at 280 K (paraelectric phase ? incommensurate phase), 135 K (incommensurate phase ? monoclinic ferroelastic phase), and 96 K (monoclinic phase ? triclinic ferroelastic phase) have been found from the temperature dependences of the spectral position and halfwidth of the low-frequency exciton band. Additional broadening of the exciton band is observed for ferroelastic phases; it is likely to be due to exciton scattering from strain fluctuations near domain walls.     

High-resolution FTIR study of the para-terphenyl phase transition at high pressure

High-resolution infrared (IR) spectroscopy has been used to investigate the pressure-induced (0-11 kbar) polymorphic phase transition of crystalline para-terphenyl at low temperature (25 K). A number of doublet bands observed in low-pressure triclinic p-terphenyl were observed to coalesce in the high-pressure monoclinic phase. The coalescing of doublet bands was attributed to changes in factor group (Davydov) splittings associated with the transition from a low-pressure triclinic phase to a high-pressure monoclinic phase. The bands that ‘disappear’ also do not correlate with frequency changes associated with changes in molecular symmetry. Molecular dynamics (MD) simulations at low temperature (20 K) yield a non-planar average molecular structure for the high-pressure monoclinic phase, in contrast to the high-temperature monoclinic phase. The MD simulations also reveal a broadening of the distribution of ring torsion angles near the triclinic-monoclinic phase transition pressure.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.     

The thermoelectric power of MEM(TCNQ)2

MEM(TCNQ)₂ undergoes a first order semiconductor to metal transition at 340.8 K. We have measured the thermoelectric power (TEP) of MEM(TCNQ)₂ in the temperature range above 335 K. Above the transition the TEP is ?65 μV/°K, in the low temperature phase it is strongly temperature dependent and approaches zero near the transition. The indicated loss of spin entropy at the transition is discussed.     

Temperature dependent microwave dielectric constant of TTF-TCNQ and related one-dimensional conductors

The results of an experimental study of the low temperature (4.2–40 K) complex dielectric constant of the organic conductors (TTF)(TCNQ), (TMTTF)(TCNQ), (DSeDTF)(TCNQ), (TSeF)(TCNQ), and the alloy (TTF)_0.97(TSeF)_0.03(TCNQ) are described. The similar features observed in these different systems suggest that a common mechanism is involved.     

Fe2P2O7 and Fe2P4O12 studied between 5–800 K

Mössbauer spectra of triclinic Fe₂P₂O₇ indicate the existence of two crystallographic metal positions in the structure. In the paramagnetic region the two Mössbauer doublets are closely overlapping. The magnetic transition takes place at ≈ 21 K and the saturated fields are around 12 tesla for the two positions. In monoclinic Fe₂P₄O₁₂ the two octahedrally coordinated metal positions give quite different quadrupole splittings (1.5 and 3 mm/s at room temperature) and hyperfine field values (42 and 12.5 Tesla at 5 K). The transition temperature is at ≈ 18.5 K.     

Model for conduction in TCNQ salts

We have extended our model for conductivity, σ, and its temperature, T, dependence to a group of molecular conductors including (Qn) (TCNQ)₂, (Adz) (TCNQ)₂ and (Adn) (TCNQ)₂. We have parametrically fit and then quantitatively calculated σ(T) for each of these materials as a product of an activated carrier concentration (600K, 450K, and 350K respectively) and a strongly T-dependent mobility determined by known electron-phonon coupling to the molecular vibrations of TCNQ.     

Thermoelectric power of ETPP (TCNQ)2 and DEPE (TCNQ)4

Results of measurements of thermoelectric power of two complexes of TCNQ, namely, ethyltriphenylphosphonium (TCNQ)₂ and 1,2 Di (N-ethyl-4-pyridinium) ethylene (TCNQ)₄ in the temperature range 100–370 K are presented. Over a certain temperature range, thermoelectric power remains independent of temperature suggesting that the most likely mechanism of charge transfer is hopping.     

Crystal and magnetic structure of single-crystal La<Subscript>1-x</Subscript><Emphasis Type="Bold">Sr</Emphasis><Subscript>x</Subscript><Emphasis Type="Bold">MnO</Emphasis><Subscript>3</Subscript><Emphasis Type="Bold">(x ≈ 1/8)</Emphasis>

A neutron powder diffraction (NPD) study on the crystal and magnetic structure of a crushed La_1-xSr_xMnO₃ (x ≈ 1/8) single crystal has been performed. The sample belongs to orthorhombic (Pnma, O) above the Jahn-Teller (JT) transition temperature (T_JT) and monoclinic (P12₁/c1, M^′) in the JT regime. We have also refined the NPD data below the charge/orbital ordering (CO/OO) temperature (T_CO/OO) with a monoclinic (P12₁/c1, M^′′) model because the experimental resolution was insufficient to clearly identify a triclinic structure. The refined lattice parameters show an obvious breathing-mode distortion between T_CO/OO and T_JT, accompanied by a large deviation of the monoclinic angle β from 90°, signifying a very strong cooperative JT distortion. A ferromagnetic (FM) moment of 3.43(5)μ _B/Mn besides an A-type antiferromagnetic (A-AFM) moment of 0.54(2) μ _B/Mn is directed mainly along the b axis in P12₁/c1 symmetry at 5 K. With increasing temperature, the A-AFM domains transform into FM ones above ~100 K and the FM spin orientation turns from the b to the c axis in crystallographic b-c plane below T_c = 187(1) K. The magnetization measurements show typical anomalies around T_CO/OO and T_JT. The measured saturation moment of 3.9(1)μ _B/Mn at 70 kOe and 5 K is well consistent with the sum 3.97(5)μ _B/Mn of the refined FM and A-AFM moments at 5 K, implying the A-AFM spins are aligned in field direction at 70 kOe. The applied magnetic field can affect the paramagnetic insulating (PMI) state in the range of magnetic polarons. Based on the size of JT distortion and the bond-valence sums (BVS’s), the CO/OO phenomenon is being discussed.     

Magnetic two-dimensional system: Manganese stearate

Magnetic susceptibility of a quasi two-dimensional magnet manganese stearate is measured between 0.05 – 80 K by a Hartshorn bridge method. The molar susceptibility follows the Curie-Weiss law in high temperature range: χ_m = 4.8/ (T + 40) (emu/mol). A transition to weak-ferromagnetic ordered state occurs at about 0.5 K, where the susceptibility maximum is observed. _χH + σ measured by the use of SQUID magnetometer indicates the appearance of spontaneous magnetization below 0.5 K. A preliminary study of a monolayer structure gives a shift of the maximum of _χH + σ to about 0.3 K.     

Specific heat and magnetic susceptibility at low temperature of two conductive TCNQ salts

The specific heat measurements between 1.4 and 4.4 K of acridinium (TCNQ)₂ and quinolinium (TCNQ)₂ salts show up a linear component; moreover, in presence of a strong magnetic field (H = 40kG), an artificial Schottky anomaly is revealed. Magnetic susceptibility experiments confirm the simultaneous existence of charge carriers, in a partially filled energy band, and localized paramagnetic centers. A standard energy band model is proposed to interpret these two properties.     

Spin-peierls transition in dimerized stacks of anion-radical salt (N-Me-2,5-di-Me-Pz)(TCNQ)2, (Pz is pyrazine)

An anion-radical salt (ARS) (N-Me-2,5-di-Me-Pz)(TCNQ)₂, where Pz is pyrazine, was synthesized and its crystal structure was resolved. X-ray diffraction experiments on single crystals were performed. Heat capacity was measured in the temperature range from 2 to 300 K. Magnetisation and magnetic susceptibility were measured in the temperature range from 2 to 300 K and the low-temperature part was measured in magnetic fields from 5 mT to 5 T. The experimental results were explained in terms of dimerized Heisenberg spin chain model. Numerical calculations were performed and compared with experimental data.     

Study of the ferrodistorsive orbital ordering in NaNiO2 by neutron diffraction and submillimeter wave ESR

NaNiO₂ has been studied by neutron-powder diffraction, magnetic susceptibility and submillimeter wave ESR. The monoclinic structure at room temperature is characterised by a ferrodistorsive orbital ordering due to the Jahn-Teller (JT) effect of the Ni³⁺ ions in the low spin state. NaNiO₂ undergoes a structural transition at around 480 K, above which the orbital ordering disappears. The high temperature phase is rhombohedral with the layered -NaFeO₂ structure ( space group). The magnetic susceptibility exhibits hysteresis and we observe a change of the Curie-Weiss law parameters above the JT transition. The anisotropy of the g-factor at 200 K can be attributed to the JT effect which favours the orbital occupation. Finally, the interplay between the magnetic and structural properties of NaNiO₂ and Li_1-xNi_1+xO₂ is discussed. Received 29 May 2000