RHF SCF 3-21G calculations are reported for the 1Σg+, 1A1, 3A′, and 1,3A″ states of simple substituted acetylenes (Y—C≡C—H, where Y = H, F, Cl,CH3, andCF3), the 1A1, 1A′, and 1.3A″ states of their Markovnikov (M) vinyl cations (Y—C+ = CH2), the 1A′ and 1.3A″ states of their anti-Markovnikov (aM) vinyl cations (YCH=C+H), and the corresponding hydrated vinyl cations. Equilibrium electronic structures and the mechanism of adiabatic protonation are described qualitatively via Lewis/resonance schematic representations of the species involved. Calculated proton affinities (PA) suggest that relative to ground state Y—C≡C—H (1Σ+/1A1), Y—C≡C—H* (1.3A″) is of greatly enhanced basicity with respect to protonation of both regiocenters. A graphical representation of the ordered pairs PA(M) versus PA(aM) as a function of substituent Y and electronic state, leads to the conclusions: (1) irrespective of both regiocenter (M/aM) and state (1Σ1+/1A1, 3A, 1.3A″) the PA's for Y—C≡C—H decrease in the order CH3 > H > Cl> F > CF3; (2) in proceeding from CH3C≡CH to CF3C≡CH, a change in protonation regiospecificity (M → aM) is experienced to approximately the same extent for both S0 and S1; (3) T2 exhibits no significant protonation regioselectivity. Critical comparison of the calculated results is made with available experimental data. An approximate picture of the energy profiles for the adiabatic hydrations of Y—C≡C—H via its ground, triplet and singlet states has been developed, based on the fixed points acetylene, vinyl cation and hydrated vinyl cation. Predicted relative reactivities of these three states are in excellent accord with available experimental data on rates of hydration. Keywords: excited states, proton transfer, photohydration.