The ionization potential of NF3: a G3 computational study on the thermochemical properties of NFx and NFx

M. Aschi and F. Grandinetti
Dipartimento di Chimica, Universit? di Roma "La Sapienza", P.le A. Moro, 5, 00185, Rome, Italy
Dipartimento di Scienze Ambientali, Universit? della Tuscia, Via S.C. De Lellis, 01100, Viterbo, Italy

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Abstract

The adiabatic ionization potential (IP) of NFx (x=1?x2013;3) and the enthalpies of formation of NFx and NFx+ have been computed using the Gaussian-3 (G3) theory. The obtained values are generally found in very good agreement with the experimental ones. However, the G3 enthalpy of formation of NF3+ at 0 K, 261.7?0.9 kcal/mol, and the adiabatic IP of NF3, 12.63?0.04 eV, differ appreciably from the experimental values of 269.6 kcal/mol and 13.00?0.02 eV, respectively, based on photoionization mass spectrometry [J. Berkowitz, J.P. Greene, J. Foropoulos, Jr., O.M. Neskovic, J. Chem. Phys. 81 (1984) 6166] and 268.2 kcal/mol and 12.94?0.01 eV, respectively, based on photoelectron photoion coincidence spectroscopy [R. R?ede, H. Troxler, Ch. Beglinger, M. Jungen, Chem. Phys. Lett. 203 (1993) 477]. This confirms the discrepancy recently noted by Ricca [A. Ricca, Chem. Phys. Lett. 294 (1998) 454] between the theoretical and the experimental adiabatic IP of NF3.

Author Keywords: G3 theory; Ionization potential; NF3