Spin relaxation of triplet pyrene in a crystal and in a glass

We have investigated the EPR spectral lines of the photo-excited triplet state of pyrene-d-10 both in a fluorene single crystal and an ethanol glass matrix. In the crystal we have measured the width, shape and saturation parameters, λ′, a and B _{1/2 ^u} , of the ΔM = 1 lines from both sites in the cleavage plane, Y-Z, at 193 K and along the principal directions, X, Y, Z, between 143 K and 300 K. In the glass the same parameters have been measured for the six resonances of the absorption derivative at 77 K. We have used a general deconvolution procedure to extract the unresolved inhomogeneous and homogeneous broadenings, ΔB _G and ΔB _L ≡ 1/γT ₂, and the spin-lattice relaxation rate, T ₁ ^-1, from λ′, a and B _{1/2 ^u} for the different types of resonances. The use of Fourier-series expansions permits optimal utilization of the data and resolution of the terms of different symmetries for these quantities. The application of the method of moments, using assumed spin densities, permits the demonstration that the main contribution to the constant term of ΔB _G, but only a small part of its anisotropy, originates from the intramolecular hyperfine interactions. As T ₂ and T ₁ are of the same order of magnitude, we have assumed the same mechanism, i.e. modulation of the fine-structure tensor D, for both relaxation effects. A first-order semi-classical treatment leads to partial agreement between the main features of the calculated and observed orientation dependences if one assumes strongly anisotropic librations coupled to large modulations of D. This is consistent with the maximal libration amplitudes estimated from the differences between the D tensors measured in the crystal and in the glass. Variations with temperature are attributed to a competition between the increase of modulation amplitudes and decrease of correlation time with heating.