Metal–carbon bond energies for adsorbed hydrocarbons from calorimetric data

Single crystal adsorption calorimetry (SCAC) is a powerful new method for measuring adsorption and reaction energies. Particularly for hydrocarbons, where little or no information is available from either experiment or theory on welldefined surfaces, this method can provide crucially needed information. Assignment of the measured calorimetric heats to the appropriate surface reaction yields directly reaction heats and heats of formation of surface species. An important extension using these results is to derive values for metal–carbon bond energies in adsorbed hydrocarbon species. In this paper we review the definition of the bond dissociation energy for a surface species and discuss methodologies and limitations for calculating accurate values of this quantity from measured calorimetric data. As a step in establishing benchmark data for adsorbed hydrocarbons, we calculate a Pt–C r bond strength, hD(Pt–C)i, of about 245kJ/mol from data for ethylidyne on Pt{111}. Two independent methods, the quasiempirical valence bond (QVB) method and an average bond energy (ABE) method, were used to obtain this value, and the two values derived from these two approaches agree quite well. We also discuss the implications and applicability of this value of D(Pt–C) for other adsorbed hydrocarbons and on other Pt surfaces, and estimates of how this bond energy should differ when the C atom s ligands are different. 2004 Elsevier B.V. All rights reserved.