Optical properties of low-dimensional organic conductors with differently oriented conducting layers: (EDT-TTF)3Hg2Br6 and (EDT-TTF)3Hg(SCN)3I0.5(PhCl)0.5

Spectral optical investigations of two low-dimensional organic molecular conductors with differently oriented conducting layers of ethylenedithiotetrathiafulvalene (EDT-TTF) molecules, namely, the (EDT-TTF)₃Hg₂Br₆ and (EDT-TTF)₃Hg(SCN)₃I_0.5(PhCl)_0.5 single crystals, have been carried out. The polarized reflectance spectra of the single crystals have been measured in the frequency range 700–6500 cm⁻¹ (0.087–0.810 eV) at temperatures from 300 to 15 K. The optical conductivity spectra have been obtained using the Kramers-Kronig relations, and their quantitative analysis has been performed in terms of a theoretical model that takes into account electron-electron correlations in the approximation of the Hubbard Hamiltonian for trimerized stacks, the vibronic coupling, and the influence of the counterion on the electronic states in the trimer. A satisfactory agreement between the theoretical and experimental spectra for both crystals made it possible to estimate the parameters of the electronic structure of the crystals in the conducting plane: the integral t of the electron transfer between the EDT-TTF molecules in the trimer, the energy U of the Coulomb repulsion between two electrons (holes) in one EDT-TTF molecule, the electron transfer damping constant γ _e , the energy shift Δ of the molecular orbital under the influence of the anions and vibronic coupling, the vibronic coupling constant g _n , and the binding energy E _p of the molecular polaron. It has been found that there are large differences in the anisotropies of the optical properties and the obtained Hubbard parameters of the electronic structure for the studied crystals.

     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Behavior of the p-T phase diagram of the organic conductor (ET)4Hg3I8

The conductivity of single crystals of the organic conductor (ET)₄Hg₃I₈ [ET-bis(ethylendithio)tetrathiafulvalene] has been investigated at temperatures from 4.2 to 360 K and pressures of up to 75 kbar. Two first-order phase transitions have been detected at room temperature at pressures of 2.75 and 6.7 kbar. On the basis of the experimental data, the p-Tphase diagram for the first-order phase transitions has been plotted. The unusual shape of the phase diagram (a slow monotonic growth of the transition temperature with a slope dT/dp=4 deg/kbar followed by a sharp drop around the point p ₀=6.5 kbar, T ₀=324 K) has been analyzed using the Landau theory of second-order phase transitions. Our analysis supports the hypothesis of a second-order phase transition around this point and also exhibits satisfactory agreement between calculations and the experimental curves of the first-order phase transitions. Zh. éksp. Teor. Fiz. 115, 2190–2196 (June 1999)     

Effect of deuteration on the electronic and electron-vibrational properties of the organic conductor k-(D8-BEDT-TTF)2[Hg(SCN)2Br]

We present here for the first time polarized reflection spectra and optical conductivity spectra of single crystals of the newly deuterated organic conductor k-(D₈-BEDT-TTF)₂[Hg(SCN)₂Br] at room temperature. The spectral region investigated is 700–40 000 cm⁻¹. We examined the effect of deuteration on electronic and electron-vibrational transitions observed in the spectra. The observed shift of the electron “dimer” transition in the infrared toward lower frequencies upon deuteration is linked with an increase in the interaction between neighboring, mutually perpendicular dimers in the structure of the deuterated crystal. A lowering of the symmetry of the BEDT-TTF molecule is demonstrated in crystals similar to k-(BEDT-TTF)₂[Hg(SCN)₂Br], relative to the symmetry D _2h of the free molecule. We refine the assignment of the spectral features determined by the interaction of electrons with the fully-symmetric intramolecular vibrations of the C=C, C-S, and C-C-H bonds of the BEDT-TTF molecule. Fiz. Tverd. Tela (St. Petersburg) 40, 1595–1598 (September 1998)     

Spin resonance of conduction electrons and EPR of localized moments in a low-dimensional organic conductor [Pd(dddt)2]Ag1.5Br3.5

The EPR spectra of a quasi-two-dimensional organic metal [Pd(dddt)₂]Ag_1.5Br_3.5 contain signals due to the spin resonance of conduction electrons (CESR) and signals due to the localized magnetic moments of Ag²⁺. The system of Ag²⁺ ions exhibits a strong indirect antiferromagnetic exchange interaction characterized by the Weiss constant Θ=−280(25) K, which leads to magnetic ordering at a temperature of T ₀=70(10) K. The same temperature T ₀ corresponds to a strong anomaly in the CESR linewidth. The observed anomaly in the CESR linewidth, as well as some features of the temperature dependence of conductivity in the system studied, are explained by the interaction between conduction electrons and Ag²⁺ ions localized in the anion layers (π-d interaction) and by antiferromagnetic ordering of the spins of Ag²⁺ magnetic ions.     

Cyclotron resonance and the de Haas-van Alfven effect in the (BEDT-TTF)8Hg4Cl12(C6H5Cl)2 organic conductor

This paper reports on measurements of the de Haas-van Alfven effect in the quasi-two-dimensional organic conductor (BEDT-TTF)₈Hg₄Cl₁₂(C₆H₅Cl)₂ performed within the temperature range 0.33–1.44 K in magnetic fields of B≤50 T. An analysis of quantum oscillations together with cyclotron resonance data obtained in the 40–120-GHz frequency range revealed that the complex quantum-oscillation spectrum is formed by the fundamental frequencies α～256 T and β～670–610 T, as well as by combination and multiple frequencies. It is shown that the character of the temperature-induced oscillation-spectrum rearrangement can be interpreted within a model taking into account the existence of a magnetic phase transition at T _c～0.9 K and the closeness of the fundamental frequency α with effective mass m*=1.48m ₀ to the spin damping condition.     

Optical properties of the proton conductor (NH2(CH3)2)2CoCl4

Based on the data from optical-spectral studies of (NH₂(CH₃)₂)₂CoCl₄ crystals, the existence of high-temperature phase transitions at 419, 380, 352, and 313 K is confirmed. It was shown that with the exception of the first transition, they are related to a considerable extent to rearrangement of the network of hydrogen bonds and are not accompanied by, considerable deformation of the lattice. In this connection the character of the electron-phonon interaction remains unchanged in the entire temperature range of the measurements. The (NH₂(CH₃)₂)₂CoCl₄ structure at room temperature is close to that of the ordered low-temperature phases of such isomorphous crystals as β-K₂SO₄. I. Franko State University, L’vov, Ukraine, 8, Kirill and Mefodii St., UA-290005, L’vov. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 412–418, May–June, 1998.     

Electronic localization in an extreme 1-D conductor: the organic salt (TTDM-TTF) [Au(mnt) ]

This article reports the investigation of a new low-dimensional organic salt, (TTDM-TTF)₂ [Au(mnt)₂], by single crystal X-ray diffraction, static magnetic susceptibility, EPR, thermopower, electrical resistivity measurements under pressure up to 25 kbar and band structure calculations. The crystal structure consists in a dimerized head to tail stacking of TTDM-TTF molecules separated by layers of orthogonal Au(mnt)₂ anions. The absence of overlap between neighboring chains coming from this particular crystal structure leads to an extreme one-dimensionality (1-D) for which the carriers of the half-filled conduction band become strongly localized in a Mott-Hubbard insulating state. This material is the first 1-D conductor in which the Mott-Hubbard insulating character cannot be suppressed under pressure. Received 15 April 2002 / Received in final form 17 June 2002 Published online 17 September 2002     

Orbital-order-induced metal-insulator transition in La(1-x)Ca(x)MnO3

We present evidence that the insulator-to-metal transition in La(1-x)Ca(x)MnO3 near x approximately 0.2 is driven by the suppression of coherent Jahn-Teller distortions, originating from d-type orbital ordering. The orbital-ordered state is characterized by large long-range Q2 distortions below T(O'- O*). Above T(O'- O*) we find evidence for coexistence between an orbital-ordered and an orbital-disordered state. This behavior is discussed in terms of electronic phase separation in an orbital-ordered insulating and an orbital-disordered metallic state.     

Mott transition from a spin liquid to a Fermi liquid in the spin-frustrated organic conductor kappa-(ET)2Cu2(CN)3

The pressure-temperature phase diagram of the organic Mott insulator kappa-(ET)2Cu2(CN)3, a model system of the spin liquid on triangular lattice, has been investigated by 1H NMR and resistivity measurements. The spin-liquid phase is persistent before the Mott transition to the metal or superconducting phase under pressure. At the Mott transition, the spin fluctuations are rapidly suppressed and the Fermi-liquid features are observed in the temperature dependence of the spin-lattice relaxation rate and resistivity. The characteristic curvature of the Mott boundary in the phase diagram highlights a crucial effect of the spin frustration on the Mott transition.     

Superconducting state of the organic conductor (TMTSF)2ClO4

(TMTSF)2ClO4 is a quasi-one-dimensional organic conductor and superconductor with Tc=1.4 K, and one of at least two Bechgaard salts observed to have upper critical fields far exceeding the paramagnetic limit. Nevertheless, the 77Se NMR Knight shift at low fields reveals a decrease in spin susceptibility chi(s) consistent with singlet spin pairing. The field dependence of the spin-lattice relaxation rate at 100 mK exhibits a sharp crossover (or phase transition) at a field Hs approximately 15 kOe, to a regime where chi(s) is close to the normal state value, even though Hc2> Hs.     

Hg(II) Selective Complexation by Chromoionophoric Calix[4]arene Derivative

The present article describes an exploration regarding Hg(II) selective complexation behavior of 5,11,17,23-tetrakis[(N,N-dimethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4). The binding affinity of 4 toward selected transition metal ions such as Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) have been investigated by UV-visible and fluorescence spectroscopies. From the results it has been noticed that 4 confers a pronounced preference for Hg(II) in complexation phenomenon even in the presence of other metal ions. The results of Job's plot analysis reveal 1:1 host-guest complex formation between Hg(II) and 4. The FT-IR spectroscopy also supports the complexation affinity of 4 for Hg(II).     

Shubnikov-de Haas oscillations spectrum of the strongly correlated quasi-2D organic metal (ET)8[Hg4Cl12(C6H5Br)2] under pressure

Pressure dependence of the Shubnikov-de Haas (SdH) oscillations spectra of the quasi-two dimensional organic metal (ET)₈[ Hg₄Cl₁₂(C₆H₅Br)₂] have been studied up to 1.1 GPa in pulsed magnetic fields of up to 54 T. According to band structure calculations, its Fermi surface can be regarded as a network of compensated orbits. The SdH spectra exhibit many Fourier components typical of such a network, most of them being forbidden in the framework of the semiclassical model. Their amplitude remains large in all the pressure range studied which likely rules out chemical potential oscillation as a dominant contribution to their origin, in agreement with recent calculations relevant to compensated Fermi liquids. In addition to a strong decrease of the magnetic breakdown field and effective masses, the latter being likely due to a reduction of the strength of electron correlations, a sizeable increase of the scattering rate is observed as the applied pressure increases. This latter point, which is at variance with data of most charge transfer salts is discussed in connection with pressure-induced features of the temperature dependence of the zero-field interlayer resistance.     

Metal-insulator transition in the low-dimensional organic conductor (TMTSF)<Subscript>2</Subscript>FSO<Subscript>3</Subscript> probed by infrared microspectroscopy

We present measurements of the infrared response of the quasi-one-dimensional organic conductor (TMTSF)₂FSO₃ along (E ) and perpendicular (E ) to the stacking axis as a function of temperature. Above the metal-insulator transition related to the anion ordering the optical conductivity spectra show a Drude-like response. Below the transition an energy gap of about 1500 cm^-1 (185 meV) opens, leading to the corresponding charge transfer band in the optical conductivity spectra. The analysis of the infrared-active vibrations gives evidence for the long-range crystal structure modulation below the transition temperature and for the short-range order fluctuations of the lattice modulation above the transition temperature. We also report about a new infrared mode at around 710 cm-1 with a peculiar temperature behavior, which has so far not been observed in any other (TMTSF)₂X salt showing a metal-insulator transition. A qualitative model based on the coupling between the TMTSF molecule vibration and the reorientation of electrical dipole moment of the FSO₃ anion is proposed, in order to explain the anomalous behavior of this new mode.