Enthalpies of formation of small free radicals and stable intermediates: Interplay of experimental and theoretical values*

A set of small radicals %SiF, %SiCl, F–%CaO, CaN–O%, %O3H, %NO3, %CH2NC, CF3O%, and O3 exhibit pronounced discrepancies between different experimental as well as experimental and calculated values of the respective enthalpies of formation DfHo(298.15). For stable molecules, this quantity is well established and reliable values are available. However, for free radicals and other short-lived intermediates, the situation is not nearly as favorable. Consequently, critical evaluation of thermodynamic properties of free radicals is necessary, both originating from experiment and computation. Calculated enthalpies of formation for the above systems are based on the ab initio methods G3MP2B3 and CCSD(T)–CBS (W1U) for which mean absolute deviations are known. q 2005 Elsevier B.V. All rights reserved.