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.
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