Application of time-variable feedback to the input amplifier of pulse magnetic resonance spectrometers: Experimental studies

Experimental research on the improvement of the sensitivity and time resolution of pulsed magnetic resonance spectrometers is discussed. It is shown that application of a time-variable feedback of a signal to the input of the receiver amplifier can decouple, the “fixed” relationship between the quality factorQ and the ringdown time of the resonance system. Experiments were performed with low-frequency, radio-frequency and microwave pulse-type magnetic resonance receivers. Modifications of an S/C-band electron spin echo modulation spectrometer carried out to check the “time-variable feedback” performance are described. It is demonstrated that the application of a time-variable feedback can significantly reduce the ringdown time and improve the recovery properties of the magnetic resonance receiver system. It is also demonstrated that the time-variable feedback can improve the overall receiver sensitivity due to the fact that the working bandwidth of the resonance system can be optimized separately for the transmitting and the receiving mode. Signal values could be increased at least three times and the signal-to-noise ratio about 1.5–2 times. The largest improvement is achieved with the initially overcoupled resonator. Experimental spectra of test samples for different settings of the time-variable feedback are shown.     

High-Frequency EPR Instrumentation

An overview of the most recent developments in high-frequency high-field electron paramagnetic resonance (EPR) instrumentation is given. In particular, the practical choices concerning sources, detectors, resonators, propagation systems as well as magnet technology are discussed in the light of various possible applications. Examples of particular homodyne and heterodyne quasi-optic EPR systems illustrate the potential for future developments in EPR technology.     

Mononuclear copper(II) complexes of bis-triazole-based macrocyclic Schiff base hydrazones: direct synthesis,EPR studies,magnetic and thermal properties

Mononuclear copper(II) complexes of 1,2,4-triazole-based Schiff base macrocyclic hydrazones, III and IV, have been reported. The prepared amorphous complexes have been characterized by spectroscopic methods, electron spray ionization mass spectrometry, and elemental analysis data. Electrochemical studies of the complexes in DMSO show only one quasi-reversible reduction wave at +0.43 V (ΔE = 70 mV) and +0.42 V (ΔE = 310 mV) for III and IV, respectively, which is assigned to the Cu(II) → Cu(I) reduction process. Temperature dependence of magnetic susceptibilities of III and IV has been measured within an interval of 2–290 K. The values of χ_M at 290 K are 1.72 × 10^?3 cm³ mol^?1 and 1.71 × 10^?3 for III and IV, respectively, which increases continuously upon cooling to 2 K. EPR spectra of III and IV in frozen DMSO and DMF were also reported. The trend g_|| > g⊥ > g_e suggests the presence of an unpaired electron in the d_x2?y2 orbital of the Cu(II) in both complexes. Furthermore, spectral and antimicrobial properties of the prepared complexes were also investigated.     

Estimation of higher-order magnetic spin interactions of Fe(III) and Gd(III) ions doped in α-alumina powder with multifrequency EPR

Fe(III) and Gd(III) ions in α-alumina (A1₂O₃) exhibit spin states ofS = 5/2 andS = 7/2 respectively. The magnitude of the zero-field interaction (ZFI) (D = 0.10?0.15 cm^?1) gives rise to an inter Kramers doublet splitting in the same order of magnitude as the X-band electron paramagnetic resonance (EPR) quantum (0.3 cm^?1). It is demonstrated that through a careful step-by-step analysis and spectral simulation of EPR spectra taken at D-band (130 GHz), Q-band (35 GHz), and X-band (9 GHz) at room temperature, the (relative) sign and magnitude of the ZFI parameters, b ₂ ⁰ , b ₄ ⁰ , and b ₄ ³ , can be reliably estimated.     

A CW and pulse EPR spectrometer operating at 122 and 244 GHz using a quasi-optical bridge and a cryogen-free 12 T superconducting magnet

A high-field continuous-wave (CW) and pulse electron paramagnetic resonance spectrometer operating at 122 and 244 GHz is described. The instrument is based on a millimeter-wave bridge built from quasi-optical components. To improve the sensitivity, a cryo-cooled detector/mixer is used. The magnetic field is generated using a cryogen-free superconducting 12 T magnet (warm bore, 88 mm) equipped with a helium-flow cryostat for sample cooling. The advantages of this spectrometer are described and first results (obtained in CW mode) on different types of samples at 122 and 244 GHz are presented. The extensions to pulse operation as well as double resonance techniques (electron-electron and electron-nuclear) are briefly discussed.     

Paramagnetic silver species in irradiated Ag−NaA zeolites. An EPR and ESEEM study

Several polymeric silver clusters have been observed in Ag_x?NaA zeolite (x=1,6) of varying water content, which was exposed to x-rays at 77 K and annealed at higher temperatures.¹⁰⁹Ag₁?NaA zeolite dehydrated at 130°C yields the dimer¹⁰⁹Ag₂ ⁺ and the trimer¹⁰⁹Ag₃ ²⁺ after irradiation at 77 K and annealing at 240 K. Owing to the use of one Ag isotope the EPR spectra of these species are highly resolved exhibitingg and hyperfine anisotropy. By irradiation of¹⁰⁹Ag_x?NaA zeolite (x=1,6) in hydrated form two new trimeric silver clusters I and II are produced. The ratio between I and II depends on the initial Ag content. ESEEM spectra of these species show interaction with aluminum nuclei of the framework and with distant water molecules. If Ag₆?NaA zeolite dehydrated at 130°C is irradiated the hexameric cluster Ag₆ ⁿ⁺ is formed. The ESEEM spectrum shows interaction only to aluminum nuclei. From ESEEM experiments on Ag₆ ⁿ⁺ with added adsorbates (D₂O, CD₃OD) it could be inferred that Ag₆ ⁿ⁺ is only stable if the neighbouring cages do not contain adsorbate molecules.