We report on the correlation of atomic concentration profiles of diffusing species with the blueshift of the quantum well luminescence from both as-grown and impurity free quantum wells intermixed on actual large optical cavity high power laser diode structures. Because it is critical to suppress catastrophic optical mirror damage, sputtered SiO2 and thermally evaporated SrF2 were used both to enhance and suppress quantum well intermixing, respectively, in these (Al) GaAs large optical cavity structures. A luminescence blueshift of 55 nm (130 meV) was obtained for samples with 400 nm thick sputtered SiO2. These layers were used to generate point defects by annealing the samples at 950 degrees C for 3 min. The ensuing Ga diffusion observed as a shifting front towards the surface at the interface of the GaAs cap and AlGaAs cladding, as well as Al diffusion into the GaAs cap layer, correlates well with the observed luminescence blue shift, as determined by x-ray photoelectron spectroscopy. Although this technique is well-known, the correlation between the photoluminescence peak blue shift and diffusion of Ga and Al during impurity free quantum well intermixing on actual large optical cavity laser diode structures was demonstrated with both x ray photoelectron and photoluminescence spectroscopy, for the first time.