The photophysics of isolated protein chromophores

Gas-phase absorption properties of chromophores of several photoactive proteins have been studied experimentally at the electrostatic heavy-ion storage ring ELISA in Aarhus. The absorption wavelength has been calculated using an augmented effective Hamiltonian technique based on the multiconfigurational quasi-degenerate perturbation theory. The results have been compared to those of widely used state-specific second-order perturbation theory formalisms and their multistate extensions and also to ground-state linear response methods. It would appear that ab initio theory is now at a stage where the intrinsic properties of the chromophore molecules may be predicted with reasonable precision. There is evidence that in terms of absorption there is almost vacuum-like conditions in the hydrophobic interior of some proteins like the green fluorescent protein (GFP). In others, like for example the visual opsins, some significant perturbations are responsible for colour tuning.