Fine structure in the transition region: Reaction force analyses of water-assisted proton transfers

Diana Yepes, Jane S. Murray, Juan C. Santos, Alejandro Toro-Labbé, Peter Politzer, Pablo Jaque

Resultado de la investigación: Contribución a una revistaArtículo

26 Citas (Scopus)

Resumen

We have analyzed the variation of the reaction force F(ξ) and the reaction force constant κ(ξ) along the intrinsic reaction coordinates ξ of the water-assisted proton transfer reactions of HX-N = Y (X,Y = O,S). The profile of the force constant of the vibration associated with the reactive mode, k ξ (ξ), was also determined. We compare our results to the corresponding intramolecular proton transfers in the absence of a water molecule. The presence of water promotes the proton transfers, decreasing the energy barriers by about 12 - 15 kcal mol-1. This is due in part to much smaller bond angle changes being needed than when water is absent. The κ(ξ) profiles along the intrinsic reaction coordinates for the water-assisted processes show striking and intriguing differences in the transition regions. For the HS-N = S and HO-N = S systems, two κ(ξ) minima are obtained, whereas for HO-N = O only one minimum is found. The k ξ (ξ) show similar behavior in the transition regions. We propose that this fine structure reflects the degree of synchronicity of the two proton migrations in each case. [Figure not available: see fulltext.]

Idioma originalInglés
Páginas (desde-hasta)2689-2697
Número de páginas9
PublicaciónJournal of Molecular Modeling
Volumen19
N.º7
DOI
EstadoPublicada - jul 2013

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Informática aplicada
  • Teoría computacional y matemáticas
  • Catálisis
  • Química orgánica
  • Química inorgánica

Huella Profundice en los temas de investigación de 'Fine structure in the transition region: Reaction force analyses of water-assisted proton transfers'. En conjunto forman una huella única.

  • Citar esto

    Yepes, D., Murray, J. S., Santos, J. C., Toro-Labbé, A., Politzer, P., & Jaque, P. (2013). Fine structure in the transition region: Reaction force analyses of water-assisted proton transfers. Journal of Molecular Modeling, 19(7), 2689-2697. https://doi.org/10.1007/s00894-012-1475-3