Abstract
A novel pulse ESR scheme for the direct measurement of hyperfine splittings is proposed. It is shown that this hyperfine spectroscopy reduces the number of the spectral lines considerably, overcomes assignment ambiguities inherent in electron-nuclear double-resonance spectra, and allows one to separate signals that overlap in ENDOR spectra. The resolution enhancement of hyperfine spectroscopy is fully utilized since the hyperfine splittings are measured between nuclear-spin rather than electron-spin transitions. The pulse sequence for the experiment is based on the chirp ENDOR method and can yield one-dimensional as well as two-dimensional spectra that correlate the ENDOR and the hyperfine frequencies. Both experiments are discussed theoretically, and the first experimental spectra of a model system are presented.
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