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• W1495860168 endingPage "8565" @default.
• W1495860168 startingPage "8558" @default.
• W1495860168 abstract "Kohn−Sham solutions are constructed from ab initio densities obtained with multireference configuration interaction (MRCI) calculations for the transition state (TS) and for the intermediate complex (IC) of the prototype symmetrical SN2 reaction F- + CH3F → FCH3 + F-. The calculated KS exchange and correlation energies, ExKS and EcKS, as well as the exchange and exchange-correlation (xc) energy densities εxKS(r) and εxcKS(r), are compared with the corresponding quantities of the standard generalized gradient approximation (GGA). GGA functionals substantially underestimate the repulsive exchange contribution to the central barrier of the SN2 reaction, thus producing a too low barrier. A similar problem arises in a number of other bonding situations, and a qualitative rule is put forward to predict success or failure of standard GGAs in molecular calculations, depending on the type of chemical bonding. For systems with two-center two-electron bonds (standard covalent bonds), two-center four-electron Pauli repulsion (interacting closed shells), and three-center three-electron bonds, current GGAs (or minor modifications) are expected to perform successfully. In these cases the GGA exchange functional represents exchange and (if it is present) nondynamical Coulomb correlation, while the GGA correlation functional represents dynamical Coulomb correlation. Contrary to this, for systems with three-center four-electron bonds (TS of the SN2 reaction), two-center three-electron bonds, and two-center one-electron bonds, for which the exchange hole is delocalized over all interacting fragments and efficient nondynamical correlation is hampered by the unfavorable electron count, the GGA exchange functionals still yield nondynamical correlation, which is in these cases spurious, the GGAs thus overestimating the relative stability of these systems." @default.
• W1495860168 created "2016-06-24" @default.
• W1495860168 creator A5029676676 @default.
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• W1495860168 date "2000-08-24" @default.
• W1495860168 modified "2023-09-24" @default.
• W1495860168 title "Comparison of the Accurate Kohn−Sham Solution with the Generalized Gradient Approximations (GGAs) for the S_N2 Reaction F^- + CH₃F → FCH₃ + F^-: A Qualitative Rule To Predict Success or Failure of GGAs" @default.
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• W1495860168 doi "https://doi.org/10.1021/jp001061m" @default.
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