Relationship of heat of chemisorption to π- and σ-level shifts as measured by photoemission

Abstract
Ultraviolet photoemission spectroscopy (UPS) has been used to study the π- and σ-level shifts of chemisorbed CO, C2H2, and C2H4 on Fe and Cu. There appears to be no correlation between these shifts and measured heats of adsorption, indicating breakdown of chemisorption theory which does not properly treat the role of the substrate in the bonding. UPS illustrates the importance of the substrate for the understanding of the bonding mechanism.

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