Performance of PNOF5 Natural Orbital Functional for Radical Formation Reactions: Hydrogen Atom Abstraction and C–C and O–O Homolytic Bond Cleavage in Selected Molecule
| Autor: | Xabier Lopez, Eduard Matito, Fernando Ruipérez, Mario Piris, Jon M. Matxain, Jesus M. Ugalde |
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| Rok vydání: | 2012 |
| Předmět: |
010304 chemical physics
Electronic correlation Chemistry Radical Ab initio Dissociació (Química) Molecular dynamics 010402 general chemistry Hydrogen atom abstraction 01 natural sciences 0104 chemical sciences Computer Science Applications Homolysis Computational chemistry 0103 physical sciences Chemistry Physical and theorical Complete active space Dinàmica molecular Química quàntica Physical and Theoretical Chemistry Bond energy Quantum chemistry Bond cleavage Fisicoquímica |
| Zdroj: | © Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 8, p. 2646-2652 Articles publicats (D-Q) DUGiDocs – Universitat de Girona instname |
| Popis: | Radical formation through hydrogen abstraction and C-C and O-O homolytic bond cleavage from selected molecules is investigated by use of natural orbital functional theory in its PNOF5 natural orbital functional implementation, and the results are compared to high-level ab initio complete active space self-consistent field (CASSCF) and complete active space with second-order perturbation theory (CASPT2) methods and experimental data. It is observed that PNOF5 is able to treat the strong electron correlation effects along the homolysis of X-H (X = C, N, O) and X-X (X = C, O) bonds, leading, in general, to the correct trends in the corresponding bond strengths and a good description of the resultant electronic structure for these radicals. In general, PNOF5 bond energies are lower than the experimental ones, because of partial lack of dynamical electron correlation. However, the part of dynamical electron correlation recovered by PNOF5 allows it to give more accurate results than CASSCF methods with a minimum window required to treat near-degeneracy effects. In addition, inspection of the natural orbital occupancies with respect to the CASSCF ones shows an outstanding performance of PNOF5 in treating degenerate and quasidegenerate states, giving a correct description of diradicals and diradicaloids formed upon C-C cleavage in cyclopropane and derivatives. |
| Databáze: | OpenAIRE |
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