Assessment of quantum chemical methods for the calculation of homolytic N–F bond dissociation energies

摘要: Abstract In this article, the performance of a wide range conventional and double-hybrid DFT methods (in conjunction with Dunning basis sets double-, triple- quadruple-zeta quality), as well number Gaussian-n thermochemical protocols are assessed for their ability to compute accurate homolytic N–F bond dissociation energies (BDEs). Their is evaluated against previously reported set 31 highly gas-phase BDEs obtained using benchmark-quality W2w protocol (See: R.J. O'Reilly, A. Karton, L. Radom, J. Phys. Chem. A 2011, 115, 5496.). Out all DFT/basis combinations investigated, ωB97 M06-2X aug'-cc-pVDZ set) offer lowest mean absolute deviations (MADs = 2.4 2.7 kJ mol–1, respectively). Of procedures, G3X offers best (MAD = 1.4 kJ mol–1), whilst significantly more economical G3X(MP2)-RAD method also excellent (MAD = 1.8 kJ mol–1).