Molecular structures of adsorbed waters at metal surfaces are essential to understanding the widespread processes ranging from ice nucleation, to water involved catalytic surface reactions, to many phenomena of biological and astrochemical importance. Instead of providing a comprehensive literature survey, we focus in this review on detailed structural information, such as water orientations and occupation sites, of intact waters at low temperatures and ultrahigh vacuum conditions investigated by various surface techniques. Despite progresses made in direct imaging the surface waters at high resolutions, as exemplified in a close-packed (e.g. Pd(111)) and an open metal surfaces (e.g. Cu(110)) supported waters, structural mysteries remain at diverse metal surfaces. We highlight experimental challenges and discuss structural mysteries in elucidating surface water structures at molecular levels.
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