Ab Initio study of H+HF2→NF(a)+HF Reaction

Abstract

Abstract: The reaction of H+NF₂→NF(a)+HF was studied by using ab initio methods.The geometries and frequencies for all species were calculated at MP2(FULL)/6-31G(d)level of theory.The energies of all species were further calculated using Gaussian 2 theory.The result implies that the reaction proceeds via an addition-elimination mechanism on the lowest singlet potential surface.The addition processes form HNF₂ molecules as the intermediates without barriers,The metastable radical NF(a)is formed by unimolecular HFelimination reactions via three-centered transition state.The best estimation of the heat of reaction is -119.4kJ/mol at 298 K. The energy of the transition state forming NF(a) is 98.4 kJ/mol lower than the reactants,The intermediate HNF₂ with an energy of 313.5kJ/mol lower than the reactants is the lowest point on the potential surface,Since the overall activation energy is negative,the title reaction is expected to be a good chemical source of NF(a)radical which was found experimentally.

Key words: Ab initio calculation, Reaction mechanism, Gaussian-2 theory

TrendMD:

GUO Jing-Zhong, DENG Cong-Hao. Ab Initio study of H+HF₂→NF(a)+HF Reaction[J]. Chem. J. Chinese Universities, 1996, 17(12): 1904.

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Ab Initio study of H+HF₂→NF(a)+HF Reaction

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