probing-structure-dynamics-interfacial-water-with-scanning-tunneling

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy

Water/solid interfaces are ubiquitous and play a key role in many environmental, biophysical, and technological processes. Resolving the internal ...

Peking University

Water/solid interfaces are vital to our daily lives and are also a central theme across an incredibly wide range of scientific disciplines. Resolving the internal structure, that is, the O-H directionality, of water molecules adsorbed on solid surfaces has been one of the key issues of water science yet it remains challenging. Using a low-temperature scanning tunnelling microscope, we report submolecular-resolution imaging of individual water monomers and tetramers on NaCl(001) films supported by a Au(111) substrate at 5 K. The frontier molecular orbitals of adsorbed water were directly visualized, which allowed discrimination of the orientation of the monomers and the hydrogen-bond directionality of the tetramers in real space. Comparison with ab initio density functional theory calculations reveals that the ability to access the orbital structures of water stems from the electronic decoupling effect provided by the NaCl films and the precisely tunable tip-water coupling. 

Real-space imaging of interfacial water with submolecular resolution.

Water-solid interactions are of broad importance both in nature and technology. The hexagonal bilayer model based on the Bernal-Fowler-Pauling ice rules has been widely adopted to describe water structuring at interfaces. Using a cryogenic scanning tunnelling microscope, here we report a new type of two-dimensional ice-like bilayer structure built from cyclic water tetramers on an insulating NaCl(001) film, which is completely beyond this conventional bilayer picture. A novel bridging mechanism allows the interconnection of water tetramers to form chains, flakes and eventually a two-dimensional extended ice bilayer containing a regular array of Bjerrum D-type defects. Ab initio density functional theory calculations substantiate this bridging growth mode and reveal a striking proton-disordered ice structure. The formation of the periodic Bjerrum defects with unusually high density may have a crucial role as H donor sites in directing multilayer ice growth and in catalysing heterogeneous chemical reactions on water-coated salt surfaces. 

An unconventional bilayer ice structure on a NaCl(001) film.

We report the quantitative assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy based on a scanning tunneling microscope. The inelastic scattering cross section was resonantly enhanced by "gating" the frontier orbitals of water via a chlorine-terminated tip, so the hydrogen-bonding strength can be determined with high accuracy from the red shift in the oxygen-hydrogen stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when a hydrogen bond is strongly coupled to the polar atomic sites of the surface. 

Nuclear quantum effects of hydrogen bonds probed by tip-enhanced inelastic electron tunneling.

The dissolution of sodium chloride (NaCl) in water is a frequently encountered process in our daily lives. While the NaCl dissolution process in liquid water has been extensively studied, whether and how the dissolution occurs below the freezing point is still not clear. Using a low-temperature scanning tunneling microscope (STM), here we were able to directly visualize the dissolution of Au-supported NaCl (0 0 1) bilayer islands by water at atomic level. We found that the single water molecule on the STM tip can assist the extraction of single Na from the NaCl surface even at 5 K, while leaving the Cl intact. When covered with a full water monolayer, the NaCl islands started to dissolve from the step edges and also showed evidence of dissolution inside the terraces as the temperature was raised up to 145 K. At 155 K, the water molecules completely desorbed from the surface, which was accompanied with the decomposition and restructuring of the bilayer NaCl islands. Those results suggest that the dissolution of NaCl may occur well below the freezing point at the ice/NaCl interfaces and is mainly driven by the interaction between the water molecules and the Na, which is in clear contrast with the NaCl dissolution in liquid water.

Atomic-scale imaging of the dissolution of NaCl islands by water at low temperature.

Scanning probe microscopy has been extensively applied to probe interfacial water in many interdisciplinary fields but the disturbance of the probes on the hydrogen-bonding structure of water has remained an intractable problem. Here, we report submolecular-resolution imaging of the water clusters on a NaCl(001) surface within the nearly noninvasive region by a qPlus-based noncontact atomic force microscopy. Comparison with theoretical simulations reveals that the key lies in probing the weak high-order electrostatic force between the quadrupole-like CO-terminated tip and the polar water molecules at large tip-water distances. This interaction allows the imaging and structural determination of the weakly bonded water clusters and even of their metastable states with negligible disturbance. This work may open an avenue for studying the intrinsic structure and dynamics of ice or water on surfaces, ion hydration, and biological water with atomic precision.

Weakly perturbative imaging of interfacial water with submolecular resolution by atomic force microscopy.

Ion hydration and transport at interfaces are relevant to a wide range of applied fields and natural processes. Interfacial effects are particularly profound in confined geometries such as nanometre-sized channels, where the mechanisms of ion transport in bulk solutions may not apply. To correlate atomic structure with the transport properties of hydrated ions, both the interfacial inhomogeneity and the complex competing interactions among ions, water and surfaces require detailed molecular-level characterization. Here we constructed individual sodium ion (Na) hydrates on a NaCl(001) surface by progressively attaching single water molecules (one to five) to the Na ion using a combined scanning tunnelling microscopy and noncontact atomic force microscopy system. We found that the Na ion hydrated with three water molecules diffuses orders of magnitude more quickly than other ion hydrates. Ab initio calculations revealed that such high ion mobility arises from the existence of a metastable state, in which the three water molecules around the Na ion can rotate collectively with a rather small energy barrier. This scenario would apply even at room temperature according to our classical molecular dynamics simulations. Our work suggests that anomalously high diffusion rates for specific hydration numbers of ions are generally determined by the degree of symmetry match between the hydrates and the surface lattice.

Article	Year
Real-space imaging of interfacial water with submolecular resolution. Nature materials\| PubMed ID: 24390380	2014
An unconventional bilayer ice structure on a NaCl(001) film. Nature communications\| PubMed ID: 24874452	2014
Nuclear quantum effects of hydrogen bonds probed by tip-enhanced inelastic electron tunneling. Science (New York, N.Y.)\| PubMed ID: 27081066	2016
Atomic-scale imaging of the dissolution of NaCl islands by water at low temperature. Journal of physics. Condensed matter : an Institute of Physics journal\| PubMed ID: 28145287	2017
Weakly perturbative imaging of interfacial water with submolecular resolution by atomic force microscopy. Nature communications\| PubMed ID: 29317638	2018
The effect of hydration number on the interfacial transport of sodium ions. Nature\| PubMed ID: 29760468	2018

Jinbo Peng

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