High resolution electronic spectra of 7-azaindole and its Ar atom van der Waals complex

Rotationally resolved fluorescence excitation spectra of the S(1)<--S(0) origin band of 7-azaindole 1H-pyrrolo(2,3-b)pyridine] and its argon atom van der Waals complex have been recorded and assigned. The derived rotational constants give information about the geometries of the two molecules in both electronic states. The equilibrium position of the argon atom in the azaindole complex is considerably different from its position in the corresponding indole complex. Furthermore, the argon atom moves when the UV photon is absorbed. There are significant differences in the intermolecular potential energy surfaces in the two electronic states. A large, vibration-state-dependent rotation of the S(1)<--S(0) electronic transition moment vector of 7-azaindole relative to that of indole suggests that these differences have their origin in S(1)/S(2) electronic state mixing in the isolated molecule, a mixing that is enhanced by nitrogen substitution in the six-membered ring.