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 original | English |
|---|---|
| Páginas (desde-hasta) | 2689-2697 |
| Número de páginas | 9 |
| Publicación | Journal of Molecular Modeling |
| Volumen | 19 |
| N.º | 7 |
| DOI | |
| Estado | Published - jul 2013 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Computer Science Applications
- Computational Theory and Mathematics
- Catalysis
- Organic Chemistry
- Inorganic Chemistry
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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.]
KW - Reaction force
KW - Reaction force constant
KW - Synchronicity
KW - Transition region
KW - Water-assisted proton transfer
UR - http://www.scopus.com/inward/record.url?scp=84879786403&partnerID=8YFLogxK
U2 - 10.1007/s00894-012-1475-3
DO - 10.1007/s00894-012-1475-3
M3 - Article
C2 - 22733272
AN - SCOPUS:84879786403
VL - 19
SP - 2689
EP - 2697
JO - Journal of Molecular Modeling
JF - Journal of Molecular Modeling
SN - 1610-2940
IS - 7
ER -