QUANTUM SCATTERING STUDIES OF LONG-LIVED RESONANCES FOR THE REACTION NE-2(+)-]NEH++H(H)

The bending-corrected rotating linear model (BCRLM) is used to investi gate the reaction of neon with H-2(+) (v=0-3) using three different fi ts to the ab initio potential-energy surface computed by Urban, Jaquet , and Staemmler. Numerous long-lived scattering resonances are found f or each surface. The number and position of these scattering resonance s are found to be sensitive to the relatively small differences among these three surfaces. These BCRLM results demonstrate how the rich res onance structure that appears in the partial cross sections is washed out in the total cross section. The integrated rates for reactivity fr om v=0 and 1 are nearly identical for all three potential-energy surfa ces over a wide range of temperatures. However, the integrated rates f rom v=2 and 3 exhibit significant differences among the potential-ener gy surfaces. A vibrationally adiabatic hyperspherical model of the tra pped resonance states provides insight into the nature and contributio n of these resonances to reactive scattering. The more accurate of the three fits to the ab initio potential-energy surface (obtained using the functional form of Aguado and Paniagua) is also used to obtain con verged results for total angular momentum J=0 employing the adiabatica lly adjusting, principal axis, hyperspherical (APH) formulation of Pac k and Parker for quantum reactive scattering in three dimensions (3D). An eigenlifetime analysis of these 3D scattering results reveals nume rous resonances with lifetimes of 1 ps or more. While this resonance s tructure is sensitive to the details of the potential energy surface, with appropriate Gaussian averaging over the total scattering energy, the cumulative reaction probabilities (CRPs) are not very sensitive to changes in the potential energy surface. Moreover, these quantum CRPs agree rather well with CRPs predicted using variational Rice-Ramsperg er-Kassel-Marcus (RRKM) calculations.