Proton transfer and internal conversion of o-hydroxybenzaldehyde:: coherent versus statistical excited-state dynamics

The intramolecular excited-state proton transfer (ESIPT) and internal conversion (IC) of o-hydroxybenzaldehyde was investigated by transient absorption measurements with 30 fs time resolution and quantitative fluorescence spectroscopy. A 45 fs delayed rise of the product emission and coherently excited vibrations indicate that the ESIPT is a ballistic motion of a well defined wavepacket along skeletal coordinates of the H-chelate ring. The IC proceeds as thermally activated process over an energy barrier of about 200 meV caused by an avoided crossing between the pipi*- and pisigma*-state. The coordinates involved in the ESIPT and in the IC are found to be orthogonal. (C) 2002 Elsevier Science B.V. All rights reserved.