Heats of formation of isomeric [C, H4, O], [C, H3, N] and [C, H5, N] radical cations |
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Authors: | Michel Sana Georges Leroy Mustapha Hilali |
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Institution: | Laboratoire de Chimie Quantique, Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium Department of Chemistry, University of Leuven, Celestijnenlaan 200 F, 3001 Leuven, Belgium |
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Abstract: | The heats of formation of six radical cations have been calculated using ab initio MO methods at the MP4/6-31 + G(2df, p) level with MP2/6-31G(d, p)-optimized geometries. The theoretical values for ΔH0f,298 (kJ/mol) of the radical ions considered are (experimental values in parentheses): methanol CH3OH+√: 854 (845); methyleneoxonium CH2OH+√2: 815 (816); methyleneimine CH2NH+√: 1076 (1054); aminomethylene HCNH+√2: 1040 (1079); methylamine CH3NH+√2: 863 (843) and methyleneammonium CH2NH+√3: 855 (958). The calculated results thus confirm the discrepancy between experiment and theory on the heats of formation of nitrogen-containing radical cations. In the latter, the distonic species are calculated to be more stable than their classical isomers. The higher stability of the distonic ions has also been discussed. The recommended heat of formation of the methyleneiminium cation CH2NH+2 is 754 kJ/mol. |
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