Thermochemistry of ammonium nitrate, NH₄NO₃, in the gas phase

Hildenbrand and co-workers have shown recently that the vapor above solid ammonium nitrate includes molecules of NH₄NO₃, not only NH₃ and HNO₃ as previously believed. Their measurements led to thermochemical values that imply an enthalpy change of D₂₉₈ = 98 ± 9 kJ mol⁻¹ for the gas-phase dissociation of ammonium nitrate into NH₃ and HNO₃. Using updated spectroscopic information for the partition function leads to the revised value of D₂₉₈ = 78 ± 21 kJ mol⁻¹ (accompanying paper in this journal, Hildenbrand, D. L., Lau, K. H., and Chandra, D. J. Phys. Chem. B 2010, DOI: 10.1021/jp105773q). In contrast, high-level ab initio calculations, detailed in the present report, predict a dissociation enthalpy half as large as the original result, 50 ± 3 kJ mol⁻¹. These are frozen-core CCSD(T) calculations extrapolated to the limiting basis set aug-cc-pV∞Z using an anharmonic vibrational partition function and a variational treatment of the NH₃ rotor. The corresponding enthalpy of formation is Δ(f)H₂₉₈°(NH₄NO₃,g) = −230.6 ± 3 kJ mol⁻¹. The origin of the disagreement with experiment remains unexplained.