Assessment of quantum chemical methods for the calculation of homolytic N–F bond dissociation energies
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Date
2016-11-01
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Chemical Data Collections
Abstract
Abstract In this article, the performance of a wide range of conventional and double-hybrid DFT methods (in conjunction with Dunning basis sets of double-, triple- and quadruple-zeta quality), as well as a number of Gaussian-n thermochemical protocols are assessed for their ability to compute accurate homolytic N–F bond dissociation energies (BDEs). Their performance is evaluated against a previously reported set of 31 highly accurate gas-phase N–F BDEs obtained using the benchmark-quality W2w thermochemical protocol (See: R.J. O'Reilly, A. Karton, L. Radom, J. Phys. Chem. A2011, 115, 5496.). Out of all of the DFT/basis set combinations investigated, ωB97 and M06-2X (in conjunction with the aug'-cc-pVDZ basis set) offer the lowest mean absolute deviations (MADs= 2.4 and 2.7kJ mol–1, respectively). Of the Gaussian-n procedures, G3X offers the best performance (MAD= 1.4kJ mol–1), whilst the significantly more economical G3X(MP2)-RAD method also offers excellent performance (MAD= 1.8kJ mol–1).
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Keywords
N-fluoro, Homolytic cleavage, Bond dissociation energy, DFT, Gaussian-n
Citation
Nuriya Akhmetova, Laura Kaliyeva, Robert J. O'Reilly, Assessment of quantum chemical methods for the calculation of homolytic N–F bond dissociation energies, In Chemical Data Collections, Volumes 5–6, 2016, Pages 28-35