Comparative electronic analysis between hydrogen transfers in the CH<inf>4</inf>/CH<inf>3</inf><sup>+</sup>, CH<inf>4</inf>/CH<inf>3</inf><sup>•</sup>, and CH<inf>4</inf>/CH<inf>3</inf><sup>-</sup> systems: On the electronic nature of the hydrogen (H<sup>-</sup>, H<sup>•</sup>, and H<sup>+</sup>) being transferred

Jordi Mestres, Miquel Duran, Juan Bertrán

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3 Citations (Scopus)

Abstract

A comparative electronic analysis of the generally termed hydrogen transfers between CH4 and the CH3+, CH3•, and CH3- fragments is presented. These systems are taken as simple models of hydride (H-), hydrogen (H•), and proton (H+) transfers between two carbon fragments (in these simple cases being modelized by two CH3+, CH3•, and CH3- fragments, respectively). The study is mainly focused on analysis of the electronic nature of the type of hydrogen being transferred in each system, and for this reason a topological analysis of charge density distributions was performed. Computation of Bader atomic charges and construction of the charge density, gradient vector field, and Laplacian of the charge density maps reveal the specific features of the electronic nature of the transferring H-, H•, and H+. Moreover, characterization of the bond critical points on the charge density surface permits clarification of the differences in atomic interactions between H-, H•, and H+ and the carbon belonging to each CH3+, CH3•, and CH3- fragment, respectively. A charge density redistribution analysis is also performed to quantify the reorganization of the electron density when going from the reactant complex to the transition state. Finally, effects of inclusion of the correlation energy at the MP2 and CISD levels are also discussed.
Original languageEnglish
Pages (from-to)1253-1262
JournalCanadian Journal of Chemistry
Volume74
Issue number6
DOIs
Publication statusPublished - 1 Jan 1996

Keywords

  • Bader density analysis
  • Electron density
  • Hydrogen transfer
  • Molecular similarity
  • Topological density analysis

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