Surface reaction kinetics on the atomic scale: studies by means of pulsed field desorption mass spectrometry

This paper reviews the development of pulsed field desorption mass spectrometry (PFDMS) towards a quantitative analytical tool for kinetic studies of elemental steps in surface chemical reactions. After a short introduction into the methodical approach, with emphasis on time-resolved studies both in the presence and in the absence of an electric field, case studies are presented including (i) the thermal equilibration of nitric oxide adsorption on Pt(111), (ii) the decomposition of methanol on Rh surfaces, and (iii) the formation of Ni–carbonyls by reaction of carbon monoxide with Ni and other transition metals. It will be demonstrated that insight into relevant mechanisms is obtained by detection of reactive intermediates and that reliable kinetic data is accessible from measurements of characteristic relaxation times.