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.
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Acknowledgments
D. Y. is grateful to Comisión Nacional de Investigación Científica y Tecnológica, Gobierno de Chile (CONICYT) for a Ph.D. fellowship. The authors acknowledge the financial support by Fondo Nacional de Desarrollo Científico y Tecnológico, Chile (FONDECYT), grant number 1100291.
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Yepes, D., Murray, J.S., Santos, J.C. et al. Fine structure in the transition region: reaction force analyses of water-assisted proton transfers. J Mol Model 19, 2689–2697 (2013). https://doi.org/10.1007/s00894-012-1475-3
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DOI: https://doi.org/10.1007/s00894-012-1475-3