Accurate quantum dynamics calculations are described for a series of three-body model systems exhibiting closely avoided crossings of potential energy surfaces in the vicinity of the reaction barrier. In particular, the surfaces show avoided crossings of bond-switching diabatic states in the vicinity of a saddle point. The dynamics calculations are carried out by linear algebraic variational methods with diabatic electronic basis functions. The coupling of electronically non-adiabatic effects to barrier crossings leads to qualitatively new kinds of quantum effects on the chemical reactivity. We find strong non-adiabatic effects on reaction probabilities due to funnel resonances with weaker effects (typically 2-20%) off resonance.
|Original language||English (US)|
|Number of pages||8|
|Journal||Journal of the Chemical Society - Faraday Transactions|
|State||Published - Mar 7 1997|