Dynamics of two-color two-photon excited fluorescence of p-terphenyl: determination and analysis of the molecular...

We present the experimental and theoretical study of the two-photon excited polarized fluorescence of p-terphenyl dissolved in cyclohexane/paraffin. The fluorescence was produced within a two-color two-photon (2C2P) excitation scheme utilizing simultaneous absorption of two femtosecond laser pulses at 400 nm and at 800 nm with the total excitation energy of 4.649 eV. The fluorescence was detected by a time correlated single photon counting (TCSPC) system with two detectors. Using different combinations of the absorbed photon polarizations we extracted seven time-dependent molecular parameters from experiment that contain all information on the dynamics of the three-photon process under study. The analysis of the obtained molecular parameter values was based on the ab initio calculations of the vertical excitation energies and transition matrix elements in p-terphenyl and allowed for determination of the whole structure of the two-photon absorption tensor, fluorescence lifetime, and the rotational correlation time. The obtained results imply that the fluorescence in the conditions of our experiment was governed mostly by the d(z) component of the fluorescence transition dipole moment that is parallel to the molecular long axis Z. The tensor was found to be symmetric. The two-photon excitation in p-terphenyl occurs simultaneously via two channels, one of them resulting in the population of the totally symmetric excited state and the other in the population of the nontotally symmetric excited state. Moreover, the energetically allowed pure electron transitions are dipole forbidden and become allowed by vibronic coupling.