Identification and properties of the 1La and 1Lb states of pyranine.

The spectroscopic locations of the 1La and 1Lb electronic states of pyranine (1-hydroxy-3,6,8-pyrenetrisulfonic acid, commonly referred to as HPTS), as well as several related compounds, are found using magnetic circular dichroism spectroscopy as well as absorption and fluorescence spectroscopies. These electronic states have been discussed in connection with the photoacid properties of HPTS. Polarization selective fluorescence spectroscopy is used to identify the transition dipole directions of the electronic states of the compounds studied. The issue of the origin for the changes in vibronic structure of HPTS in different solvents is addressed. It is demonstrated that a Brownian oscillator model, in which the strength of the coupling of the electronic states to the solvent changes with solvent, is sufficient to reproduce the trends in the shapes of the vibronic structure.