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Broadband Fourier-Transform-Detected EPR at W-Band

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Abstract

We report a true wideband Fourier transform (FT) EPR detection capability at the uniquely high frequency of 94 GHz (W-band). It is based on the quasi-optical HiPER spectrometer developed at the University of St. Andrews, into which we have integrated an arbitrary waveform generator (AWG) that is used to modulate the output from a solid-state multiplier chain prior to amplification, generating up to 1 kW microwave power with 1 GHz instantaneous bandwidth. Benchmark experiments are presented for a standard TEMPOL radical, which comprises a 500 MHz broad EPR spectrum at W-band. Using a single adiabatic chirp pulse, efficient inversion of this spectrum is demonstrated, enabling frequency-dependent studies of the longitudinal magnetization recovery in the time-domain, again via chirp pulse echo detection. From these measurements, an anisotropy in the spin–lattice relaxation time, T1, can be determined with ease for TEMPOL. In addition, we implement the FT detection scheme for multi-dimensional (electron–electron double resonance, or ELDOR) experiments, demonstrating the full capabilities of the HiPER spectrometer. As an example, we present a chirp pulse, FT-detected version of the ELDOR NMR technique for the TEMPOL radical.

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Acknowledgements

We are indebted to Rob Hunter, Paul Cruickshank, Graham Smith (St. Andrews University) for very fruitful advice and discussions, and Boris Epel (University of Chicago) for development of the software interface associated with the AWG-driven HiPER spectrometer.

Funding

This work was supported by the US Department of Energy (under DE-SC0020260 to SH). Work performed at the NHMFL is supported by the US National Science Foundation (DMR-1644779) and by the State of Florida.

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Authors and Affiliations

  1. National High Magnetic Field Laboratory, Tallahassee, Florida, USA

    Manoj Vinayaka Hanabe Subramanya, Jonathan Marbey, Krishnendu Kundu, Johannes E. McKay & Stephen Hill

  2. Department of Physics, Florida State University, Tallahassee, Florida, USA

    Manoj Vinayaka Hanabe Subramanya, Jonathan Marbey & Stephen Hill

  3. Laboratory of Physical Sciences, University of Maryland, College Park, Maryland, USA

    Jonathan Marbey

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  1. Manoj Vinayaka Hanabe Subramanya
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Contributions

SH, JM, and KK conceived the research. MVHS, JM, JEM, and KK carried out the AWG integration on the HiPER spectrometer. JEM designed and integrated the multiplier chain. MVHS and KK prepared the sample. SH, JM, MVHS, and KK designed the experiments, while MVHS and KK performed the measurements. MVHS and KK analyzed the EPR results. All authors contributed to the writing of the manuscript.

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Correspondence to Stephen Hill.

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Subramanya, M.V.H., Marbey, J., Kundu, K. et al. Broadband Fourier-Transform-Detected EPR at W-Band. Appl Magn Reson 54, 165–181 (2023). https://doi.org/10.1007/s00723-022-01499-3

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