Abstract
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) |
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Pages (from-to) | 825-832 |
Number of pages | 8 |
Journal | Journal of the Chemical Society - Faraday Transactions |
Volume | 93 |
Issue number | 5 |
DOIs | |
State | Published - Mar 7 1997 |