Electron spin resonance and quantum critical phenomena in VOx multiwall nanotubes

Basing on the high frequency (60 GHz) electron spin resonance study of the VO_x multiwall nanotubes (VO_x ‐NTs) carried out in the temperature range 4.2–200 K we report: (i) the first direct experimental evidence of the presence of the antiferromagnetic dimers in VO_x ‐NTs and (ii) the observation of an anomalous low temperature growth of the magnetic susceptibility for quasi‐free spins, which obey the power law χ (T)～1/T ^α with the exponent α ≈ 0.6 in a wide temperature range 4.2–50 K. We argue that the observed departures from the Curie–Weiss behaviour manifest the onset of the quantum critical regime and formation of the Griffiths phase as a magnetic ground state of these spin species. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron spin resonance signal of Luttinger liquids and single-wall carbon nanotubes

A comprehensive theory of electron spin resonance (ESR) for a Luttinger liquid state of correlated metals is presented. The ESR measurables such as the signal intensity and the linewidth are calculated in the framework of Luttinger liquid theory with broken spin rotational symmetry as a function of magnetic field and temperature. We obtain a significant temperature dependent homogeneous line broadening which is related to the spin-symmetry breaking and the electron-electron interaction. The result crosses over smoothly to the ESR of itinerant electrons in the noninteracting limit. These findings explain the absence of the long-sought ESR signal of itinerant electrons in single-wall carbon nanotubes when considering realistic experimental conditions.     

Electron spin resonance in superconductors

The internal field distribution in type II superconductors substantially alters the electron spin resonance g value and line shape. The resulting changes can be used to determine both the width and approximate shape of the internal field distribution.     

Electron spin resonance in polyphenylacetylene

By polymerizing phenylacetylene in the absence of initiator and in vacuo while observing electron spin resonance, it was established that the paramagnetism in the thermal polymer (PPA-T) cannot be due to interaction with oxygen but must be a property of the chemically uncontaminated macromolecule. The ESR behavior of a concentrated solution of PPA(T) in monomer and of solid (amorphous) PPA(T) displays a Curie dependence, whereas the ESR absorption of crystalline polymer made with coordination catalysts increases by one to two orders of magnitude over the temperature of about 60 to 140°C. The major portion of the XRD crystallinity disappears more sharply, at about 120°C. The paramagnetism in PPA must therefore be associated with “conformational defects” in the individual macromolecules.     

Electron spin resonance shift in spin ladder compounds

We analyze the effects of different coupling anisotropies in a spin-1/2 ladder on the electron spin resonance (ESR) shift. Combining a perturbative expression in the anisotropies with density matrix renormalization group computation of the short range correlations at finite temperature, we provide the full temperature and magnetic field evolution of the ESR paramagnetic shift. We show that for well chosen parameters the ESR shift can be in principle used to extract quantitatively the anisotropies and, as an example, discuss the material BPCB.     

Electron spin resonance investigation of ultra-small double walled carbon nanotubes embedded in zeolite nanochannels

We report on the low temperature electron spin resonance (ESR) properties of ultra-small (0.45?nm) double walled carbon nanotubes (DWCNTs) embedded in zeolite nanochannels. An isotropic ESR signal is observed at g(c)?=?2.002?77 with the spin density (S?=?1/2)?～?10(19)?g(-1), which is suggested to originate from the carbon related point defects in the DWCNTs. Measurements of the ESR line width and signal intensity as a function of temperature indicate that the spins are of a localized nature as opposed to the conduction type electrons observed in large diameter CNTs. The results are consistent with the suggestion that electrons are trapped at interstitial defects. The observed linear frequency dependence of the ESR line width of embedded DWCNTs points to 'strain' as the prime source of broadening. By contrast, the study of free standing DWCNTs shows the presence of a distinctly superlinear frequency dependence of the signal width at low temperatures. The possible origin of the frequency dependence is discussed.     

Electron spin resonance in superconducting materials

The ESR of Gd in the superconducting phase of the type II superconductors CeRu₂ and LaOs₂ shows a shift for the field for resonance and inhomogeneous broadening of the lineshape. Both effects strongly depend on the three different microwave frequencies (resp. magnetic fields). The broadening of max. 800 G is attributed to a non resolved finestructure splitting. The local field distribution in vortex state of these type II superconductors is less than 100 G and is the main contribution for shift of the field for resonance. In addition ESR results of Gd and Eu doped into La are discussed forT >T _c. The comparison of depression of the superconducting transition temperature and exchange spin-flip scattering rate determined from ESR shows a perfect agreement.     

Electron spin resonance in superconducting materials

The ESR of Gd in the superconducting phase of the type II superconductors CeRu₂ and LaOs₂ shows a shift for the field for resonance and inhomogeneous broadening of the lineshape. Both effects strongly depend on the three different microwave frequencies (resp. magnetic fields). The broadening of max. 800 G is attributed to a non resolved finestructure splitting. The local field distribution in vortex state of these type II superconductors is less than 100 G and is the main contribution for shift of the field for resonance. In addition ESR results of Gd and Eu doped into La are discussed forT >T _c. The comparison of depression of the superconducting transition temperature and exchange spin-flip scattering rate determined from ESR shows a perfect agreement.     

Electron spin resonance in pyrolyzed lignin

An investigation has been made into electron spin resonance (ESR) occurring in the ranges of carbons prepared from periodate lignin by vacuum pyrolysis. Line shape, line width, g-factors, saturation effects, and free spin concentration have been measured and the effect of oxygen on these parameters has been examined. A g-shift and lines with inhomogeneous broadening have been observed. In the presence of oxygen the lower-temperature carbons showed an unexpected increase in the detectable free spin concentration. The discussion includes factors affecting the nature of the free spins in the pyrolyzed material.     

电子自旋共振扫描隧道显微镜

单电子自旋极有可能发展成为未来信息学的基础。以电子自旋为核心的新型单分子或单原子器件将最终成为基本信息单元,基于单电子的自旋态将有可能构筑未来量子计算机的量子比特。但是,如何实现对单个电子自旋及其相干态和纠缠态的测量和控制,目前仍然是一个很大的挑战。作为调控单个电子自旋的重要实验手段,电子自旋共振扫描隧道显微镜的发展一直备受关注。文章简要介绍了电子自旋共振扫描隧道显微镜的基本概念,阐述了其发展历史和最新进展,归纳了机理探索的研究成果,论述了该设备研发面临的挑战与对策,并对未来的发展和应用做了展望。     

Electron spin resonance of proton-irradiated graphite

In the case of colossal magnetoresistance in the perovskite manganites, "double exchange" mediated by the itinerant spins is believed to play a key role in the ferromagnetism. In contrast, the conventional "Heisenberg" interaction, i.e., direct (unmediated) interaction between the localized spins produced by the proton irradiation, is identified as the origin of proton irradiation-induced ferromagnetism in graphite.     

Electron spin resonance of chromia-yttria solid solutions

Electron spin resonance spectra of chromia-yttria solid solutions have been studied at room temperature for Cr concentrations between 0.20 and 2.00 mol%. Isolated Cr³⁺ ions in sites with two different symmetries were observed, as well as well as Cr³⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Cr³⁺ ions decreases with increasing chromium concentration. The results are consistent with the assumption that the chromium ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Cr³⁺ ions of 0.64 nm, of the same order as that of Cr³⁺ ions in MgO.     

Electron spin resonance of phosphorescent fluorine-substituted aromatics

The lowest excited triplet state of the three compounds naphthalene, 1-fluoronaphthalene and 2-fluoronaphthalene, has been investigated by electron spin resonance spectroscopy. The phosphorescent molecules were oriented and diluted in durene single crystals. Zero field energies, principal values of the g tensors and hyperfine coupling constants for hydrogen and fluorine nuclei in the three canonical orientations are reported. A detailed comparative analysis of these results shows that the presence of fluorine has little effect on the π-electron distribution in the excited state. Upon substitution, some of the spin density originally present in the carbon 2pπ orbital spreads onto the fluorine atom. Spin densities on other carbon atoms remain constant. This local perturbation model is used to analyse in detail the magnetic properties of phosphorescent 1- and 2-fluoronaphthalene. From the spin densities and the experimental coupling constants, the hyperfine tensor of a C-F fragment bearing unit spin density is derived. This tensor is then broken down into four contributions which are computed using a minimum number of assumptions. The results are: (i) accurate experimental data pertaining to the nature of the C-F bond and its spin delocalization and polarization mechanisms; (ii) a firmly-established hyperfine tensor for fluorine in a planar, sp ² hybridized fragment. A simple method to determine spin densities using fluorine hyperfine structure as a probe is outlined.     

Electron spin resonance of phosphorescent fluorine-substituted aromatics

The E.S.R. spectra of triplet state 4-fluorobiphenyl in a dibenzofuran single crystal is analysed to provide further support for the ‘fluorine labelling method’ outlined in parts I and II of this series. This method is then applied to the study of some o,o'-bridged biphenyls in rigid glasses. It is confirmed that the electronic structure of all these species can be well described by that of the biphenyl triplet state. Small variations in zero-field splittings can be explained better by an inductive effect of the heteroatom on the neighbouring carbon and by a geometrical rotation of the two phenyl rings in the molecular plane rather than by a conjugation through the heteroatom.     

Electron spin resonance in X-irradiated sodium sulphate

Reliable results are reported for the various triple-dipole dispersion energy coefficients needed to evaluate the (exact) triple-dipole dispersion energy for all three-body interactions involving He, Ne, Ar, Kr, Xe, H₂, N₂, CO, O₂ and NO, and at least one molecule. A total of 645 unique coefficients, corresponding to 185 unique interactions, are considered.     

Electron spin resonance of photolytically reduced pyrazine

A mapping between the exactly soluble forced oscillator and the general vibrationally inelastic scattering problem is shown to yield a new uniform approximation based on generalized Laguerre polynomials. Computations are reported for collinear He-H₂ collisions in which H₂ is represented by harmonic and Morse oscillators. The results show that the Laguerre approximation avoids the known failings of the existing Airy and Bessel uniform approximations.     

Electron spin resonance in carbon-doped boron nitride

It is shown that carbon impurity is responsible for the yellow color and paramagnetism in boron nitride which has been heated to 1800–2300°C in graphite furnaces. The yellow BN powders exhibited 10-line ESR spectra with spin concentrations up to 10¹⁹/g. Annealing the yellow BN at 1800–2300°C in a carbon-free environment removed the yellow color and reduced the spin concentration below the observable limit of 10¹⁶/g. Such pure white BN was unaffected by prolonged irradiation with u.v., 50 kV X-rays or 1 MeV γ-rays, whereas other less pure types of BN showed a large enhancement of ESR signal after relatively short exposures to such radiation. The ESR spectra from pure white BN doped with C¹³-enriched carbon were identical to those from BN doped with normal carbon. These results suggest that the yellow color in BN is due to an F-center produced by a carbon impurity ionization mechanism. The anisotropy of the ESR was studied in carbon-doped specimens of highly oriented BN. The room temperature hyperfine splitting at 9·151 GHz was found to vary as (a + b cos²θ), where a = 7·85 ± 0·07 G and b = −1·27 ± 0·07 G. The g-value obeyed a similar relation: g = g_⊥ + Δg cos²θ, where g_⊥ = = 2·00321 ± 0·00002 and Δg = g_∥ − g_⊥ = (−9·5 ± 0·2) × 10⁻⁴.     

Electron spin resonance in nickel near Tc

The temperature dependence of the FMR and EPR linewidth of bulk nickel single crystals was measured from 260 to 410°C at 9.85 GHz. A linewidth falling off rapidly with increasing temperature was found in a region above T_c: 365<T<385°C. An interpretation by the critical behaviour of the spin system is discussed.     

Electron spin resonance spectra of radicals derived from secondary aromatic amines

The electron spin resonance spectra of diphenyl nitric oxide and the diphenylamino radical are described. Hyperfine structure in both spectra is accounted for in terms of the various interacting magnetic nuclei; the improved resolution obtained allows the coupling parameters to be given with greater precision than previous values. A mechanism is suggested for the formation of these radicals in the systems being investigated and a qualitative explanation is put forward to account for the observed variation in line width across the spectra.