title: Breakdown of the Born-Oppenheimer approximation in the F+ o-D2 -> DF + D reaction.
abstract: The reaction of F with H2 and its isotopomers is the paradigm for an exothermic triatomic abstraction reaction. In a crossed-beam scattering experiment, we determined relative integral and differential cross sections for reaction of the ground F(2P(3/2)) and excited F*(2P(1/2)) spin-orbit states with D2 for collision energies of 0.25 to 1.2 kilocalorie/mole. At the lowest collision energy, F* is approximately 1.6 times more reactive than F, although reaction of F* is forbidden within the Born-Oppenheimer (BO) approximation. As the collision energy increases, the BO-allowed reaction rapidly dominates. We found excellent agreement between multistate, quantum reactive scattering calculations and both the measured energy dependence of the F*/F reactivity ratio and the differential cross sections. This agreement confirms the fundamental understanding of the factors controlling electronic nonadiabaticity in abstraction reactions.
authors: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People's Republic of (P. R.) China.
authors: Li
authors: L
authors: Che
authors: Zefeng
authors: Z
authors: Ren
authors: Xingan
authors: X
authors: Wang
authors: Wenrui
authors: W
authors: Dong
authors: Dongxu
authors: D
authors: Dai
authors: Xiuyan
authors: X
authors: Wang
authors: Dong H
authors: DH
authors: Zhang
authors: Xueming
authors: X
authors: Yang
authors: Liusi
authors: L
authors: Sheng
authors: Guoliang
authors: G
authors: Li
authors: Hans-Joachim
authors: HJ
authors: Werner
authors: François
authors: F
authors: Lique
authors: Millard H
authors: MH
authors: Alexander