We have studied the photoexcitation dynamics of the protected gold complex Au2(SCH3)(PH3)2+1. In our calculations, we used a combination of the Delta Self-Consistent-Field method, Ehrenfest dynamics, and the time-dependent density functional theory. Our simulations provide insight into two types of mechanisms that can be tuned to enhance the photoluminescence of protected clusters in solution. Using Bader charge analysis we found that a charge transfer process between ligands appears upon excitation and that a charge transfer from the core toward the ligands takes place during the first tens of femtoseconds of the nonadibatic evolution. A later, hundreds of femtoseconds long reverse charge transfer process results in an asymmetric distribution of charge between the metal atoms. The charge redistribution and the oscillator strength of the excited-to-ground-state stimulated transition are coupled in both mechanisms. These results will help the understanding of emission properties of larger and more complex protected clusters.