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.

CAS Center for Excellence in Topological Quantum Computation University of Chinese Academy of Sciences Beijing 100190 China

Collaborative Innovation Center of Quantum Matter Beijing 100871 China

Institute of Physics The Czech Academy of Sciences Cukrovarnická 10 162 00 Prague Czech Republic

International Center for Quantum Materials School of Physics Peking University Beijing 100871 China

RCPTM Palacky University Šlechtitelů 27 783 71 Olomouc Czech Republic

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