The collective and quantum nature of proton transfer in the cyclic water tetramer on NaCl(001).

ABSTRACT

Proton tunneling is an elementary process in the dynamics of hydrogen-bonded systems. Collective tunneling is known to exist for a long time. Atomistic investigations of this mechanism in realistic systems, however, are scarce. Using a combination of ab initio theoretical and high-resolution experimental methods, we investigate the role played by the protons on the chirality switching of a water tetramer on NaCl(001). Our scanning tunneling spectroscopies show that partial deuteration of the H2O tetramer with only one D2O leads to a significant suppression of the chirality switching rate at a cryogenic temperature (T), indicating that the chirality switches by tunneling in a concerted manner. Theoretical simulations, in the meantime, support this picture by presenting a much smaller free-energy barrier for the translational collective proton tunneling mode than other chirality switching modes at low T. During this analysis, the virial energy provides a reasonable estimator for the description of the nuclear quantum effects when a traditional thermodynamic integration method cannot be used, which could be employed in future studies of similar problems. Given the high-dimensional nature of realistic systems and the topology of the hydrogen-bonded network, collective proton tunneling may exist more ubiquitously than expected. Systems of this kind can serve as ideal platforms for studies of this mechanism, easily accessible to high-resolution experimental measurements.