Effects of spin transitions degeneracy in pulsed EPR of the fullerene C70 triplet state produced by continuous light illumination

X-band echo-detected electron paramagnetic resonance (ED EPR) spectra of triplet state of fullerene C-70 generated by continuous light illumination were found to correspond below 30K to a non-equilibrium electron spin polarization. Above 30K spectra are characteristic of Boltzmann equilibrium. Spectra were simulated fairly well with zero-field splitting parameters D = 153 MHz and E and distributed within the range of 6-42 MHz. The origin of E distribution is attributed to the Jahn-Teller effect, which in glassy matrix is expected to depend on the local surrounding of a fullerene molecule (a so-called E-strain). In the center of ED EPR spectra a narrow hole was observed. With increase of the microwave pulse turning angle this hole transforms into a single narrow absorptive line. Numerical simulations by density matrix formalism confirm that central hole originates from a simultaneous excitation of both allowed electron spin transitions of the triplet (T-0 <-> T+ and T-0 <-> T-), because of their degeneracy at this spectral position. Also explanations are given why this hole has not been observed in the previously reported experiments on continuous wave EPR and on ED EPR under laser pulse excitation. (C) 2011 Elsevier B.V. All rights reserved.