Kinetics of associative detachment of O- + N2 and dissociative attachment of e- + N2O up to 1300 K: chemistry relevant to modeling of transient luminous events
PHYSICAL CHEMISTRY CHEMICAL PHYSICS(2023)
摘要
The rate constants of O- + N2 -> N2 O + e- from 800 K to 1200 K and the reverse process e- + N2 O -> O- + N2 from 700 K to 1300 K are measured using a flowing afterglow - Langmuir probe apparatus. The rate constants for O- + N2 are well described by 3 x 10-12 e-0.28 eV kT-1 cm3 s-1. The rate constants for e- + N2 O are somewhat larger than previously reported and are well described by 7 x 10-7 e-0.48 eV kT-1 cm3 s-1. The resulting equilibrium constants differ from those calculated using the fundamental thermodynamics by factors of 2-3, likely due to significantly non-thermal product distributions in one or both reactions. The potential surfaces of N2 O and N2 O- are calculated at the CCSD(T) level. The minimum energy crossing point is identified 0.53 eV above the N2 O minimum, similar to the activation energy for the electron attachment to N2 O. A barrier between N2 O- and O- + N2 is also identified with a transition state at a similar energy of 0.52 eV. The activation energy of O- + N2 is similar to one vibrational quantum of N2 . The calculated potential surface supports the notion that vibrational excitation will enhance reaction above the same energy in translation, and vibrational-state specific rate constants are derived from the data. The O- + N2 rate constants are much smaller than literature values measured in a drift tube apparatus, supporting the contention that those values were overestimated due to the presence of vibrationally excited N2 . The result impacts the modeling of transient luminous events in the mesosphere.
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