In commonly studied GFP chromophore analogues such as 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (PHBDI), the dominant photoinduced processes are cis-trans isomerization and subsequent S-1 -> S-0 decay via a conical intersection characterized by a highly twisted double bond. The recently synthesized 2-hydroxy-substituted isomer (OHBDI) shows an entirely different photochemical behavior experimentally, since it mainly undergoes ultrafast intramolecular excited-state proton transfer, followed by S-1 -> S-0 decay and ground-state reverse hydrogen transfer. We have chosen 4-(2-hydroxybenzylidene)-1H-imidazol-5(4H)-one (OHBI) to model the gas-phase photodynamics of such 2-hydroxy-substituted chromophores. We first use various electronic structure methods (DFT, TDDFT, CC2, DFT/MRCI, OM2/MRCI) to explore the S-0 and S-1 potential energy surfaces of OHBI and to locate the relevant minima, transition state, and minimum-energy conical intersection. These static calculations suggest the following decay mechanism: upon photoexcitation to the S-1 state, an ultrafast adiabatic charge-transfer induced excited-state intramolecular proton transfer (ESIPT) occurs that leads to the S-1 minimum-energy structure. Nearby, there is a S-1/S-0 minimum-energy conical intersection that allows for an efficient nonadiabatic S-1 -> S-0 internal conversion, which is followed by a fast ground-state reverse hydrogen transfer (GSHT). This mechanism is verified by semiempirical OM2/MRCI surface-hopping dynamics simulations, in which the successive ESIPT-GSTH processes are observed, but without cis-trans isomerization (which is a minor path experimentally with less than 5% yield). These gas-phase simulations of OHM give an estimated first-order decay time of 476 Is for the S-1 state, which is larger but of the same order as the experimental values measured for OHBDI in solution: 270 Is in CH3CN and 230 fs in CH2Cl2. The differences between the photoinduced processes of the 2- and 4-hydroxy-substituted chromophores are attributed to the presence or absence of intramolecular hydrogen bonding between the two rings.