Simulating the Fluorescence of the Locally Excited State of DMABN in Solvents of Different Polarities

4-(N,N-Dimethylamino)benzonitrile (DMABN) is a luminescent probe that can be used for tracking changes in the surrounding solvent due to the large change in polarity between its ground and excited states. An important characteristic of DMABN is that it exhibits dual fluorescence with two different emission energies that can be monitored, allowing for better characterization of the surrounding system. The first excited state is called the locally excited (LE) state and is characterized by the movement of charge over the conjugated ring structure. In nonpolar solvents and in the gas phase, the fluorescence of DMABN is entirely attributed to the transition from the near-planar LE state. In more polar environments, emission occurs from both the LE and a second excited state, corresponding to a twisted intramolecular charge-transfer (ICT) structure. For the sake of simplicity, this work considers transitions between only the ground and LE state. Molecular mechanical force field models of DMABN in its ground and LE states have been developed to investigate the sensitivity of the LE state to the polarity of the solvent. Both nonpolarizable and polarizable force fields were developed to simulate the molecule in a series of 10 different solvents of different polarities. The calculated Stokes shift of DMABN increases with increasing orientation polarizability of the surrounding solvent, which is the expected trend, as seen in experimental studies.