Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts

Bickelhaupt, F. Matthias

doi:10.1002/(sici)1096-987x(19990115)20:1<114::aid-jcc12>3.0.co;2-l

Cited by 546 publications

(473 citation statements)

References 160 publications

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“…One is the barrier decomposition method used by Hu et al [4][5][6] for explaining activation energy differences. The other analysis is the activaton strain model by Bickelhaupt [7][8][9]. Both decompose the system into parts in an effort to decouple some relevant interaction(s) from the others.…”

Section: Characterization Of Transition Statesmentioning

confidence: 99%

“…Fig. 2 Schematic representation of the studied association/dissociation system consisting of parts A, B, and C. Reference state used by Bickelhaupt [7][8][9], '' ''. Gas phase molecule AB and catalyst C are separate, without interaction between the two parts.…”

Section: Schematic Representation Of the System As Consisting Of Thrementioning

confidence: 99%

“…In their study on stabilization of the transition state due to interaction with a reactive complex, following the energy changes over the reaction of a dissociating methane molecule in contact with a Pd atom, de Jong and Bickelhaupt [7][8][9] have a different way to decompose the TST than described in the above section; they use the activation strain model of chemical reactivity.…”

Section: Following Components Of System-energy During a Reactionmentioning

confidence: 99%

“…5 gives the result that: Bickelhaupt [7][8][9] a E zj ABC is the difference between the transition state energy and the gas phase reference '' 00 ( Fig. 2…”

Section: Following Components Of System-energy During a Reactionmentioning

confidence: 99%

“…Subsequent papers by Hu et al [4][5][6] 1 explore in more detail the results of such decompositions for several reactions. The Bickelhaupt [7][8][9] activation strain model also decomposes the methane activation reaction. In the activation strain model, the energy of the CH bond is assumed similar to the gasphase interaction of that structure and relates to changes in the TST energy via the interaction with the reactive complex.…”

Section: Introductionmentioning

confidence: 99%

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Symmetric Transition State Analysis: An Analysis of Dissociative Methane Adsorption on Rh{111} Using Quantum Chemical Calculations

2010

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The chemical bonding aspects of the transition state (TST) of methane activation on a Rh{111} surface are analyzed. Three methods are compared: The barrier decomposition analysis of Hu et al. in which the bond between CH is assumed completely broken in the TST (Satterfield, Heterogeneous catalysis in industrial practice, 2nd ed., 1996; Chorkendorff and Niemantsverdriet, Concepts of modern catalysis and kinetics, 2003; Somorjai, Introduction to surface chemistry and catalysis, 1994); the activation strain model of Bickelhaupt in which the CH bond is assumed to be equal to the gasphase CH interaction energy (Christmann, Surface science reports, 1988; Nørs-kov and Christensen, Science, 2006; Forsberg, Chemical engineering progress, 2005); and a model in which the interaction energies between CH, and of the H atom and CH 3 with the catalyst are all given equal attention, the symmetric transition state analysis. This symmetric transition state analysis would not yield a result different from the traditional methods if all bonds were additive and decoupled. But, as our results show, that is not in general the case. The position of the maximum in non-additivity can be considered a descriptor for the position of the TST on the reaction coordinate. At the TST, we find that the three interactions are of comparable strength.

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Section: Characterization Of Transition Statesmentioning

confidence: 99%

Section: Schematic Representation Of the System As Consisting Of Thrementioning

confidence: 99%

Section: Following Components Of System-energy During a Reactionmentioning

confidence: 99%

“…5 gives the result that: Bickelhaupt [7][8][9] a E zj ABC is the difference between the transition state energy and the gas phase reference '' 00 ( Fig. 2…”

Section: Following Components Of System-energy During a Reactionmentioning

confidence: 99%