Multi-frequency rapid-scan HFEPR.

Gaining access to electron spin dynamics at (sub-)THz frequencies is highly challenging. However, this information is highly relevant for the understanding and development of spin polarization agents in dynamic nuclear polarization methods and single-molecule magnets for quantum computation. Here we demonstrate the first rapid-scan EPR experiment in 200 GHz frequency region. A voltage controlled oscillator (VCO) generated fast sinusoidal frequency sweeps with scan rates up to 3×105 THz/s after the frequency multiplication, which is equal to 107 T/s in field representation. Such high scan rates provide access to extremely short relaxation times T2=2π×sweeprate-0.5≈1 ns. The absence of a microwave cavity allowed us to perform multi-frequency experiments in the 170-250 GHz range. A further advantage of a cavity-less approach is the possibility to use vast sweeps, which in turn, allows the deconvolution using a linear sweep function. The deconvoluted spectra obtained with this method are identical to the slow-rate spectrum. We find spin-spin relaxation times of several nanoseconds for pure LiPc samples in this frequency range. These values cannot be obtained by means of conventional pulsed EPR methods.