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: Article

23 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 originalEnglish
Páginas (desde-hasta)2689-2697
Número de páginas9
PublicaciónJournal of Molecular Modeling
Volumen19
N.º7
DOI
EstadoPublished - jul 2013

Huella dactilar

Proton transfer
fine structure
protons
Water
water
Energy barriers
profiles
Protons
vibration
Molecules
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications
  • Computational Theory and Mathematics
  • Catalysis
  • Organic Chemistry
  • Inorganic Chemistry

Citar esto

Yepes, Diana ; Murray, Jane S. ; Santos, Juan C. ; Toro-Labbé, Alejandro ; Politzer, Peter ; Jaque, Pablo. / Fine structure in the transition region : Reaction force analyses of water-assisted proton transfers. En: Journal of Molecular Modeling. 2013 ; Vol. 19, N.º 7. pp. 2689-2697.
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abstract = "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.]",
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Fine structure in the transition region : Reaction force analyses of water-assisted proton transfers. / Yepes, Diana; Murray, Jane S.; Santos, Juan C.; Toro-Labbé, Alejandro; Politzer, Peter; Jaque, Pablo.

En: Journal of Molecular Modeling, Vol. 19, N.º 7, 07.2013, p. 2689-2697.

Resultado de la investigación: Article

TY - JOUR

T1 - Fine structure in the transition region

T2 - Reaction force analyses of water-assisted proton transfers

AU - Yepes, Diana

AU - Murray, Jane S.

AU - Santos, Juan C.

AU - Toro-Labbé, Alejandro

AU - Politzer, Peter

AU - Jaque, Pablo

PY - 2013/7

Y1 - 2013/7

N2 - 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.]

AB - 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.]

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