Chemical reaction dynamics beyond the Born-Oppenheimer approximation.

Abstract

To predict the branching between energetically allowed product channels, chemists often rely on statistical transition state theories or exact quantum scattering calculations on a single adiabatic potential energy surface. The potential energy surface gives the energetic barriers to each chemical reaction and allows prediction of the reaction rates. Yet, chemical reactions evolve on a single potential energy surface only if, in simple terms, the electronic wavefunction can evolve from the reactant electronic configuration to the product electronic configuration on a time scale that is fast compared to the nuclear dynamics through the transition state. The experiments reviewed here investigate how the breakdown of the Born-Oppenheimer approximation at a barrier along an adiabatic reaction coordinate can alter the dynamics of and the expected branching between molecular dissociation pathways. The work reviewed focuses on three questions that have come to the forefront with recent theory and experiments: Which classes of chemical reactions evidence dramatic nonadiabatic behavior that influences the branching between energetically allowed reaction pathways? How do the intramolecular distance and orientation between the electronic orbitals involved influence the nonadiabaticity in the reaction? How can the detailed nuclear dynamics mediate the effective nonadiabatic coupling encountered in a chemical reaction?