Energy partitioning in atom–radical reactions: The reaction of F atoms with NH2

An extension of the low-pressure infrared chemiluminescence technique has allowed the measurement of energy partitioning in the atom/radical reactions: F+NH2→HF+NH, F+ND2→DF+ND. A complete numerical model of the experiment is described in detail including its parametrization. This model allows the unambiguous determination of the primary energy distribution of the above reactions. These reactions give inverted product energy distributions, in contrast to the isoelectronic F+OH→HF+O reaction. The inverted primary energy distribution for F+NH2/ND2 indicates a direct abstraction mechanism. Ab initio quantum chemical computations on some features of the relevant potential energy surfaces support this direct abstraction route. An energetically accessible transition state, having approximately zero barrier, is found on the triplet surface which directly correlates reagents and products. The geometry of this triplet transition state is also suggestive of strong HF vibrational excitation. Abstraction on the triplet surface provides an alternative pathway to reaction on the lowest singlet surface, which contains a deep potential energy well corresponding to NH2F.