The rotationally resolved LIF spectra of four different isotopomers of the phenol-nitrogen cluster have been measured to elucidate the structural parameters of the cluster in ground and electronically excited (S-1) state. The fit of the rotational constants has been performed by a genetic algorithm and by an assigned fit to the line frequencies. The results of both methods are compared. The intermolecular structures are fit to the inertial parameters and are compared to the results of ab initio calculations for both states. This fit was performed under the restriction that the geometry of the monomer moieties do not change upon complexation. Of the remaining five intermolecular parameters two dihedral angles were fixed due to the planarity of the complex, which was inferred from the inertial defects of all isotopomers. The distance of the nearest nitrogen atom to the hydrogen atom of the phenolic hydroxy group is found to decrease upon electronic excitation of the chromophore considerably more than predicted from ab initio calculations. This deviation between theory and experiment can be traced back to the absence of electron-electron correlation in the performed complete active space self-consistent field calculations. The shortening of the OH.NN "hydrogen" bond upon electronic excitation is in agreement with the increased dipole moment of phenol in the S-1-state. (C) 2004 American Institute of Physics.