The electronic transitions that could facilitate Pd(II)-C homolytic cleavage were investigated using density functional theory (DFT) calculations using complex 1a as a representative case. Calculations were performed using various functionals (vide infra), the 6-311G++(d,p)/LANL2DZ(Pd) GD3 basis set and solvent corrected with the SMD(CHCl3) solvent model. Agreement between simulated and experimental (Figure ) UV-vis spectra was used as a criterion for computational method optimization. The general features of the spectrum are matched qualitatively in the simulated spectrum using CAM-B3LYP, including the absorbance in the 400-500 nm region, 92 that overlaps the spectral range of blue LED output. A similar absorption spectrum was observed for 2 (Figure ). The HOMO and LUMO of 1a are illustrated in Figure , which suggests the HOMO orbital is predominantly dz 2 (Pd) in character and the LUMO features dx2-y2(Pd) and σ*(Pd(II)-CH3) character. Linear time-dependent density-functional theory (TD-DFT) calculations were also performed. From these calculations the HOMO-LUMO gap was calculated to be ca. 2.72 eV, equivalent to the energy of a 456 nm photon. We postulate the relatively low energy of a dx2-y2/σ* orbital in these complexes might be facilitated by the T-shaped geometry due to the absence of a ligand trans to the methyl ligand (and associated destabilizing trans influence). Excitation leading to population of an orbital with anti-bonding character would be expected to weaken the metal-ligand bond.