Journal of Physical Chemistry A, Vol.110, No.15, 5017-5031, 2006
Fluorescence and REMPI spectroscopy of jet-cooled isolated 2-phenylindene in the S-1 state
We investigated the spectroscopy of the first excited singlet electronic state S, of 2-phenylindene using both fluorescence excitation spectroscopy and resonantly enhanced multiphoton ionization spectroscopy. Moreover, we investigated the dynamics of the S, state by determining state-selective fluorescence lifetimes up to an excess energy of similar to 3400 cm(-1). Ab initio calculations were performed on the torsional potential energy curve and the equilibrium and transition state geometries and normal-mode frequencies of the first excited singlet state (S)1 on the CIS level of theory. Numerous vibronic transitions were assigned, especially those involving the torsional normal mode. The torsional potentials of the ground and first excited electronic states were simulated by matching the observed and calculated torsional frequency spacings in a least-squares fitting procedure. The simulated S, potential showed very good agreement with the ab initio potential calculated on the CIS/6-31G(d,p) level of theory. TDDFT energy corrections improved the match with the simulated S-1 torsional potential. The latter calculation yielded a torsional barrier of V-2 = 6708 cm(-1), and the simulation a barrier of V-2 = 6245 cm(-1). Ground-state normal-mode frequencies were calculated on the B3LYP/6-31G(d,p) level of theory, which were used to interpret the infrared spectrum, the FDS spectrum of the 0(0)(0) transition and hot bands of the FES spectrum. The fluorescence intensities of the v(49) overtone progression could reasonably be reproduced by considering the geometry changes upon electronic excitation predicted by the ab initio calculations. On the basis of the torsional potential calculations, it could be ruled Out that the uniform excess energy dependence of the fluorescence lifetimes is linked to the torsional barrier in the excited state. The rotational band contour simulation of the 0(0)(0) transition yielded rotational constants in close agreement to the ab initio values for both electronic states. Rotational coherence signals were obtained by polarization-analyzed, time-resolved measurements of the fluorescence decay of the 0(0)(0) transition. The simulation of these signals yielded corroborating evidence as to the quality of the ab initio calculated rotational constants of both states. The origin of the anomalous intensity discrepancy between the fluorescence excitation spectrum and the REMPI spectrum is discussed.