Rotationally resolved fluorescence excitation spectra of the N-2 van der Waals complex of p-difluorobenzene (pDFB-N-2) have been recorded in the collision-free environment of a molecular beam. The data obtained provide information about the structure and internal motion of pDFB-N-2 in its ground (S-0) and excited (S-1) electronic states. In the ground state, the N-2 Molecule sits at R similar to 3.5 Angstrom above the ring plane, is parallel to the short axis of the ring, and undergoes hindered internal rotation about the axis perpendicular to the ring with an apparent 2-fold barrier of similar to 10 cm(-1). Excitation to the S-1 state decreases R by similar to 0.1 Angstrom and reduces the barrier to similar to 2 cm(-1). The N-2 molecule appears to have no preferred orientation in the S-1 state. Photoinduced changes in the pi-electron distribution are responsible for this behavior. Despite this fact, the S-1-S-0 transition moment orientation in pDFB is unaffected by complex formation.