Intersystem crossing (ISC) in DMABN and DMABA: Laser induced optoacoustic spectroscopy and semi-empirical (AM1) calculations

Abstract

The individual contribution of the intersystem crossing (ISC) process in the total non-radiative deactivation ofthe excited fluorophores, p-N,N-dimethylaminobenzonitrile (DMABN) and p-N,N-dimethylaminobenzaldehyde(DMABA) was determined by laser-induced optoacoustic spectroscopy (LIOAS). It was noted that, for DMABN, the ISC yield is almost insensitive to the solvent polarity, while, it is highly solvent dependent for DMABA. Semi-empirical (AM1) calculations have been performed to optimize the ground state geometry of both the fluorophores. The AM1-SCI (singly excited configuration interaction) method has been adopted to get the energies and the dipole moments of their excited states. From the calculated oscillator strengths for the optical transitions and also from absorption studies in solvents of different polarity it is revealed that DMABN isexcitedtotheS₂stateandDMABAtotheS₃stateselectivelywithalaserbeamof320nm.Theexperimental results for the large variation of the ISC yield (φ_ISC) in DMABA has been ascribed to the reordering of the nπ* and ππ* states with a change in the solvent polarity.