Аннотация:The application of action spectroscopy in connection with determination of the S0 to S1 band origin in the GFP anion model chromophore (deprotonated HBDI) is discussed. We specifically address the consequences of the lowest vibrational levels in S1 being located behind a potential-energy barrier that inhibits internal conversion to the S0 electronic ground state. Action spectroscopy based on consecutive absorption of two photons together with internal conversion will as a consequence reveal an apparent band origin that is significantly blue-shifted.