Interaction-induced localisation of protons in hydrogen bonds at superfluid helium temperatures

Abstract

It is common wisdom to expect that protons are more delocalised than much heavier nuclei due to quantum effects, for instance, in hydrogen bonds D−H^⋆ ⋅ ⋅ ⋅ A, where the shared proton H^⋆ is suspended in between the donor and acceptor heavy sites. Here, we demonstrate that this simple quasi-classical perspective fails at sufficiently low temperatures as a result of intramolecular covalent bonding accompanied by the non-covalent intermolecular interactions which induce strong localisation in the deep quantum regime. Using the water dimer as well as H₂O ⋅ ⋅ ⋅ HCl as generic models, path integral simulations at temperatures characteristic to superfluid helium conditions (about 1 K) reveal that the shared proton in such hydrogen bonds gets extremely confined to a spatial region that is comparable to – or even smaller than – that of the heavy atoms. This counter-intuitive so-called interaction-induced localisation phenomenon is also effective for the heavier nuclei, although to a much lesser extent. It is the elevated temperature (about 100 K) that restores the familiar quasi-classical picture, in which atomic spread follows the usual mass dependence of de Broglie wavelength.

Keywords:

• hydrogen bonding
• nuclear quantum effects
• quantum delocalisation
• proton transfer
• anisotropic nuclear spatial distributions

Acknowledgements

This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft as well as by the Research Department ‘Interfacial Systems Chemistry’ funded by Ruhr-Universität Bochum. The simulations have been carried out using resources from Bovilab@RUB and Rechnerverbund–NRW.