Theoretical characterization of the minimum energy path for hydrogen atom addition to N2: Implications for the unimolecular lifetime of HN2

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Abstract
The minimum energy path (MEP) for the addition of a hydrogen atom to N2 is characterized in CASSCF/externally contracted CI calculations using a [4s3p2d1f/3s2p1d] ANO basis set, with additional single point calculations at the stationary points of the potential energy surface using a [5s4p3d2f/4s3p2s] ANO basis set. These calculations represent the most extensive set of ab initio calculations on HN2 completed to date, yielding a zero‐point corrected barrier for HN2 dissociation of ≊8.5 kcal mol−1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional transition state theory and a method which utilizes an Eckart barrier to compute one‐dimensional quantum mechanical tunneling effects. This study concludes that the lifetime of the HN2 species is very short, greatly limiting its role in combustion processes.

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