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Energy Dependent Cross Sections and Nonadiabatic Reaction Dynamics in F(2P3/2, 2P1/2)+ n-HF(v,J)+H



S A. Nizkorodov, W W. Harper, W B. Chapman, B W. Blackmon, David Nesbitt


High-sensitivity direct IR laser absorption methods are exploited to investigate quantum state-resolved reactive scattering dynamics of F + n-H2(j=0,1)->HF(v,J)+H in low density crossed supersomic jets under single collision conditions. Nascent rotational state distributions and relative cross sections for reactive scattering into the energetically highest (HF(v=3,J) vibrational manifold are obtained as a function of center-of-mass collision energies from Ecom = 2.4 kcal/mole down to 0.3 kcal/mole. This energy range extends substantially below the theoretically predicted transition state barrier [Ebarrier nearly equal to} 2.9 kcal/mole,K. Stark and H. Werner, J. Chem. Phys., 104, 6515 (1996)] for the lowest adiabatic F(2P3/2) + H2 potential energy surface, therefore preferentially enhancing non-adiabatic channels due to spin orbit excited F.2P1/2) Espin orbit = 1.15 kcal/mole) in the discharge source. The HF(v = 3, J) cross sections decrease gradually from 2.4 kcal/mole down to the lowest energies investigated (Ecom nearly equal to}0.3 kcal/mole), in contrast with exact adiabatic quantum calculations which predict a rapid decrease below Ecom nearly equal to}1.9 kcal/mole and vanishing reaction probability by Ecom nearly equal to} 0.7 kcal/mol. Further evidence for non-adiabatic F.(2P1/2) reaction channel is provided by nascent rotational state distributions in HF(v=3, J), which are > 2-3 fold hotter than predicted by purely adiabatic calculations. Mostdramatically, the nascent product distributions reveal multiple HF(v=3, J) rovibrational states that would be energetically inaccessible from ground state F(2P3/2) atom reactions. These quantum state resolved reactive scattering studies provide strong evidence for non-adiabatic dynamics involving multiple potential energy surfaces, even in this well studied benchmark F + H2 reaction system.
Journal of Chemical Physics
No. 18


absorption, crossed jets, fluorine, hydrogen, non-adiabatic effects, reaction dynamics


Nizkorodov, S. , Harper, W. , Chapman, W. , Blackmon, B. and Nesbitt, D. (1999), Energy Dependent Cross Sections and Nonadiabatic Reaction Dynamics in F(<sup>2</sup>P<sub>3/2</sub>, <sup>2</sup>P<sub>1/2</sub>)<sup>+</sup> n-HF(v,J)+H, Journal of Chemical Physics (Accessed June 4, 2023)
Created October 31, 1999, Updated October 12, 2021