We present semiempirical AM1 calculations for the ground and excited state of 2-naphthol and some of its cyano derivatives in the gas phase. Following photoexcitation, the Mulliken electron density on the oxygen diminishes slightly for the acid and more conspicuously for the anionic conjugated base. This agrees with the measured solvatochromic parameters for 2-naphthol. In both electronic states, we find a nice correlation with the measured pK values in water. The electronic charge distribution on the distal ring of the anion agrees with the experimental acidity order in both S-0 and S-1. Upon excitation, it increases predominantly in positions 3, 5, and 8. The ring system of the anion assumes an alternant quinoidal structure in the ground state of the anion, which becomes more symmetric in the relaxed excited state, This suggests that the enhanced aromatic character of a 4n electron system in the excited state allows for better delocalization of the oxygen charge within the ring.