The Liouville formalism in frequency space is used in the present study to investigate the effect of the intramolecular coupling on the four wave mixing signal (FWM) of a two-level system. The internal rovibrational structure is incorporated by including the spin-orbit residual interaction in the total Hamiltonian of the system. The behavior of the FWM signal as a function of the coupling parameters (v and V0) has been studied. The main properties affected were the permanent and transition dipole moments of the solute molecules when the rotating wave approximation is neglected. Reduced polarization expressions are obtained from the resonant terms and from the larger coherence and population density contributions to the macroscopic polarization, which in turn allows us to characterize individual resonances in the resulting frequency spectrum. © 2002 Elsevier Science (USA).