Recently (I) we presented a general method for calculating ENDOR spectra of a randomly oriented polycrystalline (powder) S = 4 paramagnet (2, 3) that has g and hyperfme tensors of arbitrary symmetry and relative orientation. That study (Paper I) laid a foundation for the detailed analysis of polycrystalline ENDOR spectra, as well as for the heuristic categorization of such spectra, much as EPR spectra long have been classified (isotropic, axial, rhombic (4)). To this end the calculations in I used a “double delta function” approach, employing a-function EPR and ENDOR component lineshapes. They showed that polycrystalline ENDOR spectra can exhibit a rich array of features when the static field is set to a g value where the EPR signal arises from a well-defined set of orientations of the paramagnet, rather than a single crystal-type setting. The principal values and relative orientation of a hyperline tensor can be obtained by examining such angle-selected spectra obtained as the observing g value (static field) is moved across the EPR envelope. We now have generalized the analysis to permit full simulations of polycrystalline ENDOR spectra by including finite EPR and ENDOR component linewidths. The calculations presented here show that the two types of features that arise in the double delta-function limit, divergences and maxima, both persist as absorption peaks in the full simulations. These ENDOR peaks broaden equally as the ENDOR component linewidth, W,,, increases, but in general they do not broaden equally as the EPR component linewidth, W,, increases. Instead, the rate at which a peak broadens with W, is related to (&/dg), the rate of change in its ENDOR frequency with observing g value. The essential features of the approach developed in I are first summarized, and then are extended to include EPR and ENDOR component linewidths. When the external field is set to an arbitrary value, Ho, within a a-function EPR envelope, the EPR signal intensity, and thus an ENDOR signal, arises from the selected molecular orientations associated with the curve on the unit sphere, S, comprising points for which the orientation dependent spectroscopic splitting factor, g = g(B, @), has a fixed value defined by the strength of the observing field: gmi, < g = hv/@& < g,,,. H’owever, although g is constant over the locus of points, S, in general the angledependent hyperfine coupling, A = A(& 4), is not, and the ENDOR pattern in general is more complex than a single crystal-like spectrum. The net ENDOR intensity at radiofrequency, Y, is determined by the sum of the probabilities that the
Read full abstract