Article révisé par les pairs
Résumé : The transition between the diabatic and the adiabatic zero order representation when the electronic potential coupling increases, is studied in the partitioning method (PM) and in the complex coordinate method (CCM) implemented in a discrete variable representation (DVR). The model is a C + type predissociation in a diatomic system with a crossing between a Morse potential energy curve and an exponentially repulsive curve. In the weak coupling regime (isolated diabatic metastable states), both methods confirm the linear variation of the resonance widths with the strength of the electronic interaction, as expected in a perturbative treatment. When the coupling is large in the diabatic representation (strong overlap regime), the formation of narrow resonances supported by the upper adiabatic potential can be related, in PM, to the process of avoided resonance overlapping among interfering states. The complete change of representation can be described in the initial diabatic basis set in PM. However, the full energy dependence of the discrete-continuous matrix elements must then be taken into account. The deformation and the final splitting of a diffuse spectral line .with increasing coupling is re-examined in terms of these energy dependent eigenvalues of the effective Hamiltonian. The use of the appropriate representation, either diabatic or adiabatic, according to the strength of the electronic coupling, has been found decisive in CCM so as to observe the correct migration of the resonance positions towards the zero order adiabatic states, and the decrease of their widths. No relevant results have been obtained for the intermediate strength of the coupling in CCM. Analytical expressions for the derivative coupling matrix elements (∂/∂R) in the fixed node DVR (corresponding to the particle-in-a-box wave functions) have been established. © 1996 American Institute of Physics.