A quantum and semiclassical study of dynamical resonances in the C+NO- CN+O reaction

摘要

Accurate quantum mechanical reactive scattering calculations were performed for the collinear C+NO—~CN±O reaction using a polynomial-modified London Eyring Polanyi Sato (PQLEPS) potential energy surface (PBS), which has a 4.26 eV deep well in the strong interaction region, and a reference LEPS PBS, which has no well in that region. The reaction probabilities obtained for both PESs show signatures for resonances. These resonances were characterized by calculating the eigenvalues and eigenvectors of the collision lifetime matrix as a function of energy. Many resonances were found for scattering on both PESs, indicating that the potential well in the PQLEPS PBS does not play the sole role in producing resonances in this relatively heavy atom system and that Feshbach processes occur for both PESs. However, the well in the PQLEPS PBS is responsible for the differences in the energies, lifetimes, and compositions of the corresponding resonance states. These resonances are also interpreted in terms of simple periodic orbits supported by both PESs (using the WKB formalism), to further illustrate the role played by that potential well on the dynamics of this reaction. The existence of the resonances is associated with the dynamics of the long-lived CNO complex, which is much different than that of systems having an activation barrier. Although these results were obtained for a collinear model of the reaction, its collinearly-dominated nature suggests that related resonant behavior may occur in the real world.