Rotationally resolved electronic spectroscopy of tryptamine conformers in a supersonic jet

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Abstract
We have observed the high resolution fluorescence excitation spectrum of the molecule tryptamine in the gas phase. At low resolution the spectrum contains six features which have been assigned as the origins of different conformers of the tryptamine molecule. At high resolution the rotational structure in each of these features has been resolved, and the rotational structure of five of the features has been analyzed. This analysis has provided information about the geometries of the different conformers. Two conformers, labeled A and F, have the amino group of the molecule g a u c h e to the indole ring, while conformer D has the amino group nearly eclipsed by the indole ring. Conformer B has a rotational structure identical to that of conformer A, while the rotational structure of conformer E is identical to that of conformer D. It is suggested that the pairs of conformers with identical rotational structure are related to each other by rotation about the Cα–N bond, such a rotation moving only hydrogen atoms. Feature C consists of two overlapped conformers, and it is suggested that these conformers have the amino group t r a n s to the indole ring. The direction of the transition moment is measured for five of the conformers and is found to be identical for all conformers within the precision of the measurement. The direction of the transition moment indicates that the transition is to the 1 L b excited electronic state.

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