Nuclear quantum effects in protonated water clusters
Michele Casula  1@  , Félix Mouhat  2  , Sandro Sorella  3  , Rodolphe Vuilleumier  4  , Antonino Marco Saitta  5  
1 : Institut de minéralogie, de physique des matériaux et de cosmochimie  (IMPMC)  -  Website
Museum National d'Histoire Naturelle, Université Pierre et Marie Curie - Paris 6 : UM120, Institut de recherche pour le développement [IRD] : UR206, Centre National de la Recherche Scientifique : UMR7590
Tour 23 - Barre 22-23 - 4e étage - BC 115 4 place Jussieu 75252 PARIS -  France
2 : École Normale Supérieure, 24 Rue Lhomond, 75005 Paris, France
Ecole Normale Supérieure de Paris - ENS Paris
3 : SISSA, via Bonomea 265, 34136 Trieste, Italie
4 : École Normale Supérieure, 24 Rue Lhomond, 75005 Paris, France
École normale supérieure [ENS] - Paris
5 : IMPMC, Sorbonne Université, 4 Place Jussieu, Paris
Sorbonne Université UPMC Paris VI

Water is a key ingredient for life and plays a central role as solvent in many biochemical reactions. However, the intrinsically
quantum nature of the hydrogen nucleus, revealing itself in a large variety of physical manifestations, including proton transport, is
still elusive. Here we study, by an unprecedented combination of state-of-the-art quantum Monte Carlo methods and
path-integral molecular dynamics, the structure and hydrogen-bond dynamics of the protonated water hexamer, the fundamental unit for the hydrated proton. We show that nuclear quantum effects and thermal ones cooperate to produce an unexpected non-monotonic behavior of the hydrogen-bond length as a function of temperature. This behavior can be explained by an inverse Ubbelohde effect, as it results from quantum delocalization of the hydrated proton across two water molecules upon temperature rise. The corresponding hydrogen bond is the shortest precisely around 250-300 K. As a consequence, room temperature is revealed to be the ``sweet spot'' for proton transport and diffusion, and thus for many phenomena depending on proton transport, including life.


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