A critical review is presented of the results of (experimental) quantitative structural studies of molecular reaction intermediates at surfaces; i.e. molecular species that do not exist naturally in the gas phase and, in most cases, are implicated in surface catalytic processes. A brief review of the main experimental methods that have contributed to this area is followed by a summary of the main results. Investigated species include: carboxylates, RCOO– (particularly formate, but also deprotonated amino acids); methoxy, CH3O–; carbonate, CO3; ethylidyne, CH3C–; NHx and SOx species; cyanide, CN. As far as possible in the limited range of systems studied, a few general trends are identified
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