ABSTRACT
In high-frequency electron paramagnetic resonance (EPR) spectroscopy the sample is usually accommodated in a single-mode cylindrical TE(011) microwave cavity. This cavity stands out in terms of flexibility for various types of EPR experiments due to convenient control of its resonance frequency and easy waveguide-to-cavity microwave coupling. In continuous wave and in pulsed EPR it is, however, essential to be able to vary the coupling efficiency over a large range. We present a new mechanical design to vary the microwave coupling to the cavity using a movable metal sphere. This coupling sphere is shifted in the plane of the iris wall inside the coupling waveguide. The design allows for a compact and robust construction of the EPR probehead that can be easily accommodated inside a limited space of helium flow cryostat. The construction details and characterization of the coupling element for 95 GHz (W-band) EPR as well as for 34 GHz (Q-band) are presented.
ABSTRACT
The use of a rapid stepping of the magnetic field for investigation of electron dipole-dipole ESEEM in pulsed X-band ELDOR is described. The magnetic field jump, synchronized with a microwave pumping pulse, is positioned between the second and the third pulses of the stimulated echo pulse sequence. This echo is measured as a function of the delay between the first and the second pulses. The data are analyzed for a Fourier transform resulting in a Pake resonance pattern. To remove the electron-nuclear contributions to ESEEM, time traces with pumping were divided by those without. This resulted in complete elimination of electron-nuclear contributions, which is seen from the absence of peaks at nuclear frequencies and the similarity of results for protonated and deuterated solvents. For increasing the electron-electron modulation depth, a scanning of the magnetic field during the microwave pumping is proposed. The interspin distances and their distribution are determined for two long-chained (ca. 2 nm) nitroxide biradicals in glassy toluene and in frozen nematic liquid crystal 4-cyano-4'-pentyl-biphenyl. For the latter solvent, the alignment of the axis connecting two nitroxides in biradicals is quantitatively analyzed.
