A comparison of pulse and CW EPR T2-relaxation measurements of an inhomogeneously broadened nitroxide spin probe undergoing Heisenberg spin exchange

Nitroxide spin probes are inhomogeneously broadened (IHB) by intramolecular hyperfine interactions with protons (deuterons) producing lines of Voigt shape. Thus, to study T2 relaxation by continuous wave (CW) EPR, the Voigt must be deconvoluted to find the Lorentzian component. For homogeneously broadened lines, T2 is obtained directly from the Lorentzian line widths DHLpp; however, for IHB lines finding T2 from DHLpp is more complicated. It has been known for many years that values of DHLpp of high precision may be obtained from IHB lines; however, direct, accurate comparison of spin exchange frequencies obtained from electron spin echo decay and CW EPR data has been lacking. It is demonstrated here that despite complications in the interpretation of experiments, these two techniques yield the same spin exchange rate constant for spin probes that are the most difficult to treat. (c) 2023 Elsevier Inc. All rights reserved.