Concerted ultrafast time-resolved spectroscopic experiments and ab initio computational (TDDFT) studies of the electronic transitions of 4-fluoro-N,N-dimethylaniline (FDMA) have been performed to investigate the mechanism of photo-induced intramolecular charge transfer (ICT). The compound FDMA shows dual fluorescence from a pi pi* state and a closely-lying twisted intramolecular charge transfer (TICT) state in both n-hexane and acetonitrile. The very similar lifetimes observed for the two emission bands indicate that the pi pi* and the TICT states are effectively in thermal equilibrium at room temperature. (C) 2013 Elsevier B.V. All rights reserved.