Abstract
Resonant two-photon ionization (R2PI) and fluorescence spectra of the 1-naphthol·H2O and 1-naphthol-d1·D2O cluster are reported and interpreted with emphasis on intracomplex vibrational energy redistribution (IVR) and vibronic coupling. The analysis included an ab initio normal-coordinate calculation of both complexes at the 6-31G (d,p) level. In S1 ← S0 R2PI spectra, the intermolecular modes were found to be very weak; only one such S1 vibration was observed at 57 cm-1 (54 cm-1 for 1-naphthol-OD·D2O). At excitations less than 400 cm-1 above the S1← S0 origin, the fluorescence spectra retain a simple 1-naphthol-like pattern. At higher excess energies, the fluorescence exhibits complex structure due to emission from both relaxed and unrelaxed S1 vibrational states, showing efficient coupling through the hydrogen bond. This restricted IVR behavior changes to dissipative IVR at about 834 cm-1 above the S1 ← S0 origin. Exceptions to general IVR are observed. The S1 + 403 cm-1 level is a restricted IVR case, w...
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