The nature of hydrated proton on solid surfaces is of vital importance in electrochemistry, proton channels, and hydrogen fuel cells but remains unclear because of the lack of atomic-scale characterization. We directly visualized Eigen- and Zundel-type hydrated protons within the hydrogen bonding water network on Au(111) and Pt(111) surfaces, using cryogenic qPlus-based atomic force microscopy under ultrahigh vacuum. We found that the Eigen cations self-assembled into monolayer structures with local order, and the Zundel cations formed long-range ordered structures stabilized by nuclear quantum effects. Two Eigen cations could combine into one Zundel cation accompanied with a simultaneous proton transfer to the surface. Moreover, we revealed that the Zundel configuration was preferred over the Eigen on Pt(111), and such a preference was absent on Au(111).

Water structures at electrolyte/electrode interfaces play a crucial role in determining the selectivity and kinetics of electrochemical reactions. Despite extensive experimental and theoretical efforts, atomic-level details of ion-specific water structures on metal surfaces remain unclear. Here we show, using scanning tunneling microscopy and noncontact atomic force microscopy, that we can visualize water layers containing alkali metal cations on a charged Au(111) surface with atomic resolution. Our results reveal that Li⁺ cations are elevated from the surface, facilitating the formation of an ice-like water layer between the Li⁺ cations and the surface. In contrast, K⁺ and Cs⁺ cations are in direct contact with the surface. We observe that the water network structure transitions from a hexagonal arrangement with Li⁺ to a distorted hydrogen-bonding configuration with Cs⁺. These observations are consistent with surface-enhanced infrared absorption spectroscopy data and suggest that alkali metal cations significantly impact hydrogen evolution reaction kinetics and efficiency. Our findings provide insights into ion-specific water structures on metal surfaces and underscore the critical role of spectator ions in electrochemical processes.

The dynamics of glass-forming systems shows a multitude of features that are absent in normal liquids, such as non-exponential relaxation and a strong temperature-dependence of the relaxation time. Connecting these dynamic properties to the microscopic structure of the system is challenging because of the presence of the structural disorder. Here we use computer simulations of a metallic glass-former to establish such a connection. By probing the temperature and wave-vector dependence of the intermediate scattering function we find that the relaxation dynamics of the glassy melt is directly related to the local arrangement of icosahedral structures: Isolated icosahedra give rise to a liquid-like stretched exponential relaxation whereas clusters of icosahedra lead to a compressed exponential relaxation that is reminiscent to the one found in a solid. Our results show that in metallic glass-formers these two types of relaxation processes can coexist and give rise to a dynamics that is surprisingly complex.

Using linear scaling theory, we study the behavior of response functions extrema in the vicinity of the critical point. We investigate how the speed of convergence of the loci of response function extrema to the Widom line depends on the parameters of the linear scaling theory. We find that when the slope of the coexistence line is near zero, the line of specific heat maxima does not follow the Widom line but instead follows the coexistence line. This has relevance for the detection of liquid-liquid critical points, which can exhibit a near-horizontal coexistence line. Our theoretical predictions are confirmed by computer simulations of a family of spherically symmetric potentials.