Torsional band assignment and intramolecular twist potential of 9,9rsquo;hyphen;bianthryl and its 10hyphen;cyano derivative in a free jet

摘要

Using a pulsed supersonic beam and laserhyphen;induced fluorescence spectroscopy the torsional structure of theS0andS1states of 9,9rsquo;hyphen;bianthryl (BA) and its derivative 10hyphen;(cyano)hyphen;9,9rsquo;hyphen;bianthryl (CBA) was investigated. Taking into account the very different equilibrium positions of theS0andS1potentials which result in a nonobservable 0ndash;0 transition within the jet spectra, a new and straightforward procedure of torsional band assignment is carried out. This is based on a characteristic pattern of Franckndash;Condon factors within the dispersed fluorescence spectra. The torsional potentials were determined by a fit procedure of a onehyphen;dimensional model to the experimental data. The results show that theS1double minimum potential for BA is shallower than for CBA indicating a stronger interaction between the molecular halfs of the latter compound. The observed rotational contours of torsional bands recorded for CBA reflect the change from a symmetric top molecule (for states above theS1torsional barrier) to an asymmetric top (for states below the barrier) and manifest the tunneling splitting of the level just below the barrier. The dispersed fluorescence spectra of CBA are discussed in terms of intramolecular vibrational redistribution (IVR) processes. The measured fluorescence decay rates as a function of excess vibrational energy of CBA reflect a saturation behavior already within the origin region in contrast to BA (saturation near 380 cmminus;1). This is tentatively ascribed to a low lying dark background state possibly of charge transfer character.