Using density functional theory (DFT) and linear and quadratic response time-dependent DFT, we investigated the structure and optical properties of a silver sulfide cluster with the interesting property of dual emission that was observed when in crystal form but not in solution. Since the dual fluorescence is observed only in the crystal, a supposition of stabilization of a higher-energy excited state by an excimer-like complex was analyzed by calculations for a cluster dimer, formed through pi-stacking of aromatic groups bonded to the sulfur atoms. However, because of the complexity of the system, a simple one-dimensional method for dimer optimization, which works moderately well in predicting the red-shifted fluorescence compared to its absorption in a naphthalene dimer, predicts only partially the red shift for the emission energy. Interestingly, calculations of the two-photon absorption (TPA) cross-section on the optimized isolated cluster as well as the crystal structure geometry indicate significant off-resonance TPA. While some materials have significantly larger TPA cross-sections, such a TPA cross-section off-resonance could be useful. The high density of States in the dimer system results in a higher probability for significant resonance enhancement and thus much larger TPA cross-sections.