Hyperfine anomaly arising from the nuclear spin-forbidden transition,and absolute sign determination of the zero-field splitting constant

It has been found in the triplet E.S.R. spectra of radical pairs in irradiated potassium deuterium fumarate that the hyperfine structure of the two transitions, M _s = 1?0 and M _s = 0?+1, are entirely different. This anomaly has been interpreted in terms of the forbidden transition arising from the mixing of the nuclear spin states by the anisotropic hyperfine interaction. The theory has been developed for multiplet electron spin systems and includes the nuclear Zeeman interaction which is often neglected. The theoretical predictions are in good agreement with the observed separations and intensities of the anomalous hyperfine lines. In addition, it has been found that since the forbidden lines of the electron spin multiplet system with S ≥ 1 appear strongly only in transitions which include some specific electronic spin states, the anomalous features of the spectra make it possible to determine the absolute sign of the zero-field or hyperfine splitting constant, if the sign for one of them is known. Using this principle, attempts have been made to determine the absolute sign of the zero-field splitting constant for a number of triplet E.S.R. spectra which exhibit a hyperfine anomaly arising from the proposed mechanism.