On the short and long phosphorescence lifetimes of aromatic carbonyls

Abstract

Abstract This work applies theoretical and computational methods to investigate the relationship between phosphorescence lifetime and the electronic character of the lowest triplet state of aromatic carbonyls. A formal analysis of the spin-perturbed wave functions shows that phosphorescence is due to a direct spin-orbit coupling mechanism modulated by permanent dipoles when the T1 minimum is 3nπ*. If the minimum is a totally symmetric 3ππ*, phosphorescence is due to an indirect spin-orbit coupling mechanism involving transition dipole moments with other excited states. The magnitude difference between permanent and transition dipoles leads to a much faster 3nπ* phosphoresce than 3ππ* if vibronic coupling effects are not considered. These predictions were verified with phosphorescence lifetime simulations of benzaldehyde and its three derivatives in the gas phase employing a vertical approximation as well as the nuclear ensemble approach. Both simulation methods deliver good results for molecules with a 3nπ* T1 minimum. Nevertheless, vertical simulations fail for those molecules with a 3ππ* T1 minimum due to the overwhelming importance of vibronic couplings.