High-resolution spectroscopy of weak and short-lived bands of the S(1) 1B(3u) <-- S(0) 1A(g) transition of naphthalene.

Rotationally resolved high-resolution spectra and fluorescence decay curves have been observed for weak and short-lived vibronic bands of the S(1) (1)B(3u) <-- S(0) (1)A(g) transition of naphthalene. Fluorescence lifetime of the vibronic band with an excess energy of 1390 cm(-1) (0(0)(0) + 1390 cm(-1) band) is remarkably shorter than that of other bands. Zeeman splitting of rotational lines is very small, so that the main radiationless process is not intersystem crossing to the triplet state but internal conversion to the ground state. The lifetime is thought to be governed by the strength of vibronic coupling between vibrational levels of the S(0) and S(1) states. As for the 0(0)(0) + 2570 cm(-1) band, energy shifts were found in only a few rotational levels although the excess energy was higher than the threshold of intramolecular vibrational redistribution. We conclude that all of the rotational levels are mixed with other vibrational levels. The 0(0)(0) + 3068 cm(-1) band spectrum is fairly complicated with numerous rotational lines, which is attributed to strong vibronic coupling with the S(2) (1)B(2u) state.