Skip to Main content Skip to Navigation
Journal articles

Wrapping Up Hydrophobic Hydration: Locality Matters

Abstract : Water, being the universal solvent, acts as a competing agent in fundamental processes, such as folding, aggregation or biomolecular recognition. A molecular understanding of hydrophobic hydration is of central importance to understanding the subtle free energy differences, which dictate function. Ab initio and classical molecular dynamics simulations yield two distinct hydration water populations in the hydration shell of solvated tert-butanol noted as “HB-wrap” and “HB-hydration2bulk”. The experimentally observed hydration water spectrum can be dissected into two modes, centered at 164 and 195 cm–1. By comparison to the simulations, these two bands are attributed to the “HB-wrap” and “HB-hydration2bulk” populations, respectively. We derive a quantitative correlation between the population in each of these two local water coordination motifs and the temperature dependence of the solvation entropy. The crossover from entropy to enthalpy dominated solvation at elevated temperatures, as predicted by theory and observed experimentally, can be rationalized in terms of the distinct temperature stability and thermodynamic signatures of “HB-wrap” and “HB-hydration2bulk”.
Document type :
Journal articles
Complete list of metadata

https://hal-univ-evry.archives-ouvertes.fr/hal-02959973
Contributor : Sana Bougueroua <>
Submitted on : Wednesday, October 7, 2020 - 11:50:59 AM
Last modification on : Friday, April 30, 2021 - 10:22:07 AM

Links full text

Identifiers

Collections

Citation

V. Conti Nibali, S. Pezzotti, F. Sebastiani, D. Galimberti, G. Schwaab, et al.. Wrapping Up Hydrophobic Hydration: Locality Matters. Journal of Physical Chemistry Letters, American Chemical Society, 2020, 11 (12), pp.4809-4816. ⟨10.1021/acs.jpclett.0c00846⟩. ⟨hal-02959973⟩

Share

Metrics

Record views

60