Absorption spectra of the fully oxidized bCcO crystal studied. In this work (A) versus those of bCcO obtained in free solution (B). A, spectra a and b were obtained before and after the first X-ray exposure, respectively; spectra c and d were obtained from the same crystal following annealing before and after the second X-ray exposure, respectively. Spectrum e is a reference spectrum of a fully reduced ligand-free crystal. The upper right inset displays an expanded view of spectrum a (top) and b (bottom) showing the presence of the broad band at ∼900 nm associated with CuA in the cupric state in spectrum a, which is absent in spectrum b. bCcO, bovine heart CcO.