화학공학소재연구정보센터
Journal of Chemical Physics, Vol.108, No.15, 6331-6341, 1998
Effects of complex formation on low energy H++O-2(X-3 Sigma(-)(g),v=0)-> H+O-2(+)(X-2 Pi(g),v '') charge transfer
The mutual effects of complex formation and nonadiabatic transitions in a low energy ion-molecule collision are investigated. This is achieved by studying the exothermic charge transfer (CT) process H++O-2(X (3) Sigma(g)(-),v=0)-->H+O-2(+)(X (2) Pi g,v ") at collision energies below the first vibrational excitation threshold (E<0.2 eV). State-to-state vibronic CT cross sections are thus computed in the quantal infinite order sudden approximation using diabatic electronic states of Grimbert et nl. [Chem. Phys. 124, 187 (1988)] and a vibrational basis of 14-reactant and 15-product states. The characteristics of the (H-O-2)(+) interaction potential in the entrance channel allow the formation of both translation-to-vibration and orbiting complexes which reflect themselves in the quantal scattering as Feschbach and shape resonances, respectively. The charge transfer may occur either directly or by a sort of predissociation of these complexes. The strong anisotropy of the relevant interactions in the (H-O-2)(+) system enables one to explore these effects in a broad range of coupling conditions. Two cases appear which are considered in detail : one in which CT cross sections are small while the electron transfer interaction is important, and the other in which the CT cross sections are large while the electron transfer interaction is rather small. Structures in the rotationally averaged cross section emphasize privileged orientations of the molecule for the studied CT process.