Pulsed-High Field/High-Frequency EPR Spectroscopy

Abstract. Pulsed high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is used to disentangle many kinds of different effects often obscured in con-tinuous wave (cw) EPR spectra at lower magnetic fields/microwave frequencies. While the high magnetic field increases the resolution of G tensors and of nuclear Larmor fre-quencies, the high frequencies allow for higher time resolution for molecular dynamics as well as for transient paramagnetic intermediates studied with time-resolved EPR. Pulsed EPR methods are used for example for relaxation-time studies, and pulsed Electron Nuclear DOuble Resonance (ENDOR) is used to resolve unresolved hyperfine structure hidden in inhomogeneous linewidths. In the present article we introduce the basic concepts and selected applications to structure and mobility studies on electron transfer systems, reaction centers of photosynthesis as well as biomimetic models. The article concludes with an introduction to stochastic EPR which makes use of another concept for investigating resonance systems in order to increase the excitation band-width of pulsed EPR. The limited excitation bandwidth of pulses at high frequency is one of the main limitations which, so far, made Fourier transform methods hardly feasible.