Fluorescence and ultraviolet absorption spectra, and the structure and vibrations of 1,2,3,4-tetrahydronaphthalene in its S1(pi,pi*) state

The ultraviolet absorption spectra in the static vapor phase and the laser induced fluorescence spectra (both fluorescence excitation and single vibronic level fluorescence spectra) of jet-cooled 1,2,3,4-tetrahydronaphthalene have been used along with theoretical calculations to assign many of the vibronic levels in the S1(pi,pi*) state. These have been compared to the corresponding vibrational levels for the S0 ground state. Analysis of the upper states of the ring-twisting vibration nu(31) and three other low-frequency modes has allowed us to construct an energy map of the lowest vibrational quantum states for both S0 and S1. The molecule is highly twisted in both electronic states with high barriers to planarity, which are calculated to be 4811 cm(-1) for S0 and 5100 cm(-1) for S1. However, the experimental data show that the barrier should be lower in the S1 state.