The photo darkening (PD) absorption spectra from unseeded amplifier operation (by 915 nm pumping) of ytterbium/aluminum and codoped silica fibers is after prolonged operation observed to develop a characteristic line at 2.6 eV (477 nm). This line is proposed to be due to inter center excitation transfer from type II oxygen deficiency centers ODC(II) to Tm3+ trace impurities. The ODC(II) is proposed to be the result of a displacive transition of a 4-fold silica ring hosting two 3-fold silicon units that presents two non-bridging oxygen to Yb3+ (as part of its 6-fold coordination by oxygen). The displacive transition is initiated by a charge disproportionation process which leads to NBO transfer in forming dioxasilirane (2-fold coordinated silicon with two NBO attached) next to silylene (2-fold coordinated silicon with a lone electron pair). In collaboration with a valence electron of Yb 3+ a new 1/2/11/2 chemical bond is formed on dioxasilirane which comprises the PD color center for the visible and near-infrared. Difference in solid acidity of the silica material co-doped with Yb/Al and Yb/P may explain the observed difference in spectral shapes by change of bond order to the formed chemical bond. © 2011 Optical Society of America.