Magnetic resonance of intrinsic defects in the spin-Peierls magnet CuGeO3

Magnetic resonance in pure single-crystal CuGeO₃ at frequencies 9–75 GHz in the temperature range 1.2–25 K is investigated. Splitting of the magnetic-resonance line into several spectral components is observed at temperatures below 5 K, where spin-Peierls dimerization suppresses the magnetic susceptibility and the ESR signal intensity. Analysis of the magnetic resonance spectra over a wide frequency range with different directions of the magnetic field at different temperatures makes it possible to identify among these components the ESR signals due to defects, having effective spin S=1/2 and spin S=1, in the spin-Peierls phase. The g factor corresponding to these ESR signals is the same and close to the value characteristic for the ion Cu²⁺. Another magnetic-resonance line is characterized by a strongly anisotropic g factor and an increase (at a threshold in the excitation power) in the susceptibility both at resonance and in the line wings. These signals are tentatively attributed to two possible types of planar defects arising on the walls of domains of the spin-Peierls state with different values of the dimerization phase. Zh. éksp. Teor. Fiz. 114, 1876–1896 (November 1998)     

Magnetic properties of defects in spin-gap magnets

The magnetic properties of defects were studied in spin-gap magnets such as spin-Peierls magnet CuGeO₃, Haldane magnet PbNi₂V₂O₈, and charge-ordered ladder magnet NaV₂O₅. Doping of these systems with nonmagnetic impurities leads to additional magnetic degrees of freedom, which manifest themselves at low temperatures, where the intrinsic magnetic susceptibility of a spin-gap system is close to zero. Magnetic susceptibility appears due to the local destruction of the singlet ground state as a result of impurity-induced breakage of spin chains. Antiferromagnetically correlated areas arise near the spin-chain breaks. The sizes of these areas and the effective spin of these specific spin clusters are estimated. The order parameter and its spatially modulated depth are determined for impurity-induced magnetically ordered phases. The magnetic properties of defects for the NaV₂O₅ ladder structure are explained in the model of electrons “hopping” near the chain break. The hopping degree of freedom effectively influences the total spin of a spin-chain fragment and magnetization of the system.     

Anomalous thermal conductivity of single crystal Cu2Te2O5Cl2

A strong increase of the thermal conductivity is observed at the phase transition (T _c=18.2 K) in Cu₂Te₂O₅Cl₂ single crystal. This behavior is compared with that of the spin-Peierls system NaV₂O₅, where a similar experimental observation has been made, and the conventional spin-Peierls system CuGeO₃, where a modest kink in the thermal conductivity curve has been observed. The strong increase of the thermal conductivity atT _c in Cu₂Te₂O₅Cl₂ could be partially attributed to the opening of the energy gap in the magnetic excitation spectrum evident from the magnetic susceptibility measurements. However, the main reason for the anomaly of the thermal conductivity could be explained by a strong spin-lattice coupling in this system, which what is in agreement with the preliminary X-band electron spin resonance measurement.     

Quasi-one-dimensional spin chains in CuSiO3: an EPR study

Temperature-dependent electron paramagnetic resonance (EPR) studies were performed on CuSiO₃. This recently discovered compound is isostructural with the spin-Peierls compound CuGeO₃. The EPR signals show characteristics different from those of CuGeO₃ and are due to Cu²⁺ spins located along quasi one-dimensional chains. ForT>8.2 K the spin susceptibility closely follows the predictions of anS=1/2 one-dimensional Heisenberg antiferromagnet withJ/k _B=21 K. BelowT=8.2 K the spin susceptibility immediately drops to zero indicating long-range magnetic order.     

Thermal conductivity of the spin-Peierls compound CuGeO3

The thermal conductivity of the pure and zinc-doped spin-Peierls compound CuGeO₃ is investigated for the first time. Characteristic features reflecting the changes in the phonon spectrum of the crystals are observed in the k(T) curves at a transition into the dimerized state in CuGeO₃ at T _sp =14.2 K and in Cu_0.98Zn_0.02GeO₃ at T _sp =10.6 K. Near the spin-Peierls transition temperature T _sp the thermal conductivity of Cu_0.98Zn_0.02GeO₃ (k=3 W/m·K) is much less than the thermal conductivity of CuGeO₃ (k=21.5 W/m·K). Pis’ma Zh. éksp. Teor. Fiz. 66, No. 12, 823–826 (25 December 1997)     

Magnetic properties of the low dimensional spin system (VO)PO:ESR and susceptibility

Experimental results on magnetic resonance (ESR) and magnetic susceptibility are given for single crystalline (VO)₂P₂O₇. The crystal growth procedure is briefly discussed. The susceptibility is interpreted numerically using a model with alternating spin chains. We determine J =51 K and . Furthermore we find a spin gap of meV from our ESR measurements. Using elastic constants no indication of a phase transition forcing the dimerization is seen below 300 K. Received: 22 December 1997 / Accepted: 17 March 1998     

ESR millimeter-band spectroscopy of magnetic ordering in the low-dimensional magnet CuGeO3

Resonant absorption of microwaves in CuGeO₃ single crystals in a frequency band of 40 to 120 GHz, in magnetic field B⩽15 T, at temperatures ranging between 0.5 and 300 K, and in the configuration B∥a has been investigated. Several absorption lines (S ₀, S _a, and S _b) whose parameters strongly depend on temperature have been detected close to ESR. The temperature dependence of the total absorption in the main line S ₀ with the Landé g-factor g ₀=2.154 at temperatures above the spin-Peierls transition temperature is in good agreement with Bonner and Fisher’s theoretical prediction for a one-dimensional Heisenberg spin chain. In addition to the main resonance, a resonance of smaller amplitude, S _a, with the g-factor g _a=2.72 has been detected at temperatures ranging down to a characteristic temperature T≃1 K, below which the amplitude of this feature drops to zero. A radical restructuring of the magnetoabsorption spectrum occurs at the temperature of the spin-Peierls transition T _SP≈14 K. At T<12 K new features emerge in the spectrum, namely, a broad absorption line overlapping with the narrow lines S ₀ and S _a, and a line S _b with g _b=1.83, which is not detected at temperatures above T _SP. An analysis of amplitudes and total absorption of ESR lines as functions of temperature has shown that the temperature range below 1 K is anomalous, which may be caused by an additional ordering in the CuGeO₃ magnetic subsystem at low temperatures. Zh. éksp. Teor. Fiz. 112, 1727–1738 (November 1997)     

Appearance of new lines and change in line shape in the IR spectrum of a NaV2O5 single crystal at a spin-Peierls transition

New lines are observed in the infrared spectrum of a crystal due to unit-cell doubling at a spin-Peierls transition (in NaV₂O₅). The change in the shape of the spectral lines at the spin-Peierls transition is recorded. A contour characteristic of a Fano resonance is observed above the transition temperature T _sp and the standard symmetric contour is observed below T _sp . We attribute this effect to the opening of a gap in the magnetic-excitation spectrum at the spin-Peierls transition. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 9, 711–716 (10 May 1997)     

Monte-Carlo study of correlations in quantum spin chains at non-zero temperature

Antiferromagnetic Heisenberg spin chains with various spin values (S=1/2,1,3/2,2,5/2) are studied numerically with the quantum Monte-Carlo method. Effective spin S chains are realized by ferromagnetically coupling n=2S antiferromagnetic spin chains with S=1/2. The temperature dependence of the uniform susceptibility, the staggered susceptibility, and the static structure factor peak intensity are computed down to very low temperatures, . The correlation length at each temperature is deduced from numerical measurements of the instantaneous spin-spin correlation function. At high temperatures, very good agreement with exact results for the classical spin chain is obtained independent of the value of S. For the S=2 chain which has a gap , the correlation length and the uniform susceptibility in the temperature range are well predicted by the semi-classical theory of Damle and Sachdev. Received: 23 December 1997 / Revised and Accepted: 11 March 1998     

Cu-isotope effect on the spin-Peierls transition of CuGeO3

The Cu-isotope effect on the spin-Peierls transition temperature T _SP in samples of the Cu²⁺ linear-chain compound CuGeO₃ has been determined by dc-magneticsusceptibility and specific-heat measurements. A downshift of the spin-Peierls transition by about 0.1 K for the ⁶⁵Cu-isotope enriched ⁶⁵CuGeO₃ as compared to ^natCuGeO₃ containing the natural mixture of isotopes is found consistently in the magnetization and specific heat. This result suggests different isotope effects on the phonon characteristic frequency θ₀ on the one hand and on the spin-phonon coupling constant g on the other hand. However, the isotope effect on T _SP is smaller than estimated if all atoms were to contribute to ω₀ and only the Cu atoms to g.     

Spin dynamics in CuGeO3 studied by muon spin rotation

We report a muon spin rotation (SR) study of the magnetic properties of the Cu²⁺ quasi-one-dimensional CuGeO₃ system and its lightly-doped derivative Cu_0.97Zn_0.03GeO₃. Susceptibility measurements on CuGeO₃ show a sudden change in the vicinity of 14 K that has been interpreted before as a magnetic transition to a spin-Peierls state. SR shows no evidence of spin freezing below 14 K, implying that the transition is to a magnetic state with no static (random or ordered) electronic moments. A modest slowing down of the electronic spin dynamics is also identified at this temperature. Similarly, no evidence of a transition to a static magnetic state is found for Cu_0.97Zn_0.03GeO₃ whose susceptibility shows hysteretic behaviour between zero-field and field cooled measurements at 4 K, previously ascribed to spinglass-like behaviour. Given the nature of the muon spin as a local magnetic probe, the present results necessitate a re-interpretation of the origin of the susceptibility anomaly observed in the doped system.     

Specific heat of the spin-Peierls compound CuGeO3

The specific heat of the quasi-onedimensional magnetic compound CuGeO₃ shows a sharp anomaly at the spin-Peierls transition temperatureT _sp . The experimental decrease of the magnetic specific heat belowT _sp indicates the presence of a spin gap as observed previously with inelastic neutron scattering. A magnetic field of 6T suppressesT _sp only slightly but reduces the spin gap by a factor of two.     

Submillimeter wave esr and far infrared spectroscopy measurements of CuGeO3

Submillimeter wave ESR and far infrared transmission measurements of first inorganic spin-Peierls system CuGeO₃ have been performed using the single crystals. Our new results are discussed in connection with the magnetic properties of the spin-Peierls systems and the recent neutron measurements of CuGeO₃.     

Pseudo-gap and possible Spin-Peierls transition in the vanadium oxide VOSb 2 O 4

We report on the magnetic susceptibility and electron spin resonance measurements on polycrystalline samples of the vanadium oxide VOSb₂O₄, a quasi-one-dimensional S = 1/2 Heisenberg system. The susceptibility vanishes at zero temperature, but there is no cusp at the onset of the susceptibility drop, and the ESR linewidth exhibits an increase characteristic of a phase transition at a much lower temperature. We show that this behaviour is consistent with the formation of a pseudo-gap in a spin-Peierls system in the adiabatic limit. Received 7 February 2001 and Received in final form 24 April 2001     

Microscopic interactions in CuGeO 3 and organic Spin-Peierls systems deduced from their pretransitional lattice fluctuations

CuGeO₃ exhibits a Spin-Peierls (SP) transition, at T _SP = 14.3 K, which is announced above 19 K by an important regime of one-dimensional (1D) pretransitional lattice fluctuations which can be detected until about 40 K using X-ray diffuse scattering investigations. A quantitative analysis of this scattering shows that in this 1D direction the correlation length follows the “universal” behaviour expected for the thermal fluctuations of a real order parameter which characterizes the lattice dimerization. This allows to define a 1D mean-field temperature, T _SP ^MF , of about 60 K and invalidates any mean field scenario for the SP transition of CuGeO₃. As T _SP ^MF is as high as 4 T _SP we propose that the 3D-SP order is achieved by the interchain coupling between 1D solitons which form below about 16-20 K. CuGeO₃ being in the non-adiabatic regime, it is also suggested that the observed pretransitional fluctuations of CuGeO₃ originate from the X-ray scattering on a very broad damped critical response of lower frequency than the “critical” phonon modes. From the quantitative analysis of the 1D fluctuations we also estimate the microscopic parameters of the SP chain. These parameters allow to locate CuGeO₃ close to the quantum critical boundary separating the gapped SP ground state to the ungapped anti-ferromagnetic ground state. The vicinity of a quantum critical point emphasizes the role of the quantum and non-adiabatic fluctuations and the importance of the interchain coupling in the physics of CuGeO₃. Finally we compare these findings with those obtained for the organic SP systems (BCPTTF)₂PF₆, (TMTTF)₂PF₆ and MEM(TCNQ)₂. From a similar analysis of the pretransitional lattice fluctuations it is found that (BCPTTF)₂PF₆ and (TMTTF)₂PF₆ are located on the SP gapped classical-quantum boundary and are in the adiabatic regime where the fluctuations lead to the formation of a pseudo-gap in the spin degrees of freedom. Differently, we place MEM(TCNQ)₂ inside the SP quantum phase around the crossover line between the adiabatic and non-adiabatic regimes. Received 13 September 2000 and Received in final form 6 February 2001     

New polarization effect and collective excitation in S = 1/2 quasi-one-dimensional antiferromagnetic quantum spin chain

Anomalous polarization characteristics of magnetic resonance in CuGeO₃ doped with 2% Co impurity are reported. For the Faraday geometry, this mode is damped for the microwave field B _ω aligned along a certain crystallographic direction, showing that the character of magnetic oscillation differs from the standard spin precession. The observed resonance coexists with the ESR on Cu²⁺ chains; it is argued not to be caused by “impurity” EPR, as previously claimed, but to correspond to a previously unknown collective mode of magnetic oscillations in an S = 1/2 AF quantum spin chain. The text was submitted by the authors in English.     

The smooth structural change in mesoscopic Peierls chains

We investigate the Peierls transition in finite chains by exact (Lanczos) diagonalization and within a seminumerical method based on the factorization of the electron-phonon wave function (Adiabatic Ansatz, AA). AA can be applied for mesoscopic chains up to micrometer sizes and its reliability can be checked self-consistently. Our study demonstrates the important role played for finite systems by the tunneling in the double well potential. The chains are dimerized only if their size N exceeds a critical value N_c which increases with increasing phonon frequency. Quantum phonon fluctuations yield a broad transition region. This smooth Peierls transition contrasts not only to the sharp mean field transition, but also with the sharp RPA soft mode instability, although RPA partially accounts for quantum phonon fluctuations. For weak coupling the dimerization disappears below micrometer sizes; therefore, this effect could be detected experimentally in mesoscopic systems. Received: 3 January 1998 / Revised: 13 March 1998 / Accepted: 3 April 1998     

Electron hopping and optic phonons in Eu3S4

Raman scattering on single crystals of Eu₃S₄ does not show the allowed q=o phonon modes in the cubic phase and exhibits no new modes in the distorted low temperature phase (T<186 K). Above the Curie temperature T_c=3.8 K the scattering is dominated by a spin-disorder induced one-phonon density of states allowing for the observation of the zone boundary phonon breathing mode of the S^2?ions. This mode does not show any anomaly near the charge order -disorder phase transition T_t=186 K. Temperature tunable spin fluctuations associated with the temperature activated Eu²⁺→Eu³⁺ electron hopping are detected in the scattering intensity, superimposed on the usual thermal spin disorder.