Carbon monoxide quantum chemical calculations

The Dotz reaction mechanism has received further support from kinetic and theoretical studies. An early kinetic investigation [37] and the observation that the reaction of the metal carbene with the alkyne is supressed in the presence of external carbon monoxide [38] indicated that the rate-determining step is a reversible decarbonylation of the original carbene complex. Additional evidence for the Dotz mechanistic hyphotesis has been provided by extended Hiickel molecular orbital [23, 24] and quantum chemical calculations [25],... 

Carbon monoxide carbo-mers [5-7], i.e., monoxides of linear odd carbon chains longer than one C 0 n = 3, 5, 7, 9...), are highly reactive molecules suggested as potential constituents of interstellar and circumstellar gas clouds. Considerations based on MO theory and quantum chemical calculations indicate that, similar to pure odd carbon chains, all these heterocumulenes are singlet carbenes in the ground state [93]. Since its matrix isolation in 1971 [94] and its synthesis in gas phase in 1983 [95], the simplest member of this family, i.e., tricarbon monoxide C3O, has been extensively studied both experimentally and theoretically [96-102], and its interstellar presence fully confirmed [103]. In particular, on the basis of... 

L. M. Kustov, V. B. Kazansky, S. Beran, L. Kubelkova, and P. Jiru, Adsorption of carbon monoxide on ZSM - 5 zeolites infrared spectroscopic study and quantum - chemical calculations, J. Phys. Chem. 91, 5247-5251 (1987). 

Shubina, T.E. and Koper, M.T. (2002) Quantum-chemical calculations of CO and OH interacting with bimetallic surfaces. Electrochim. Acta, 47, 22—23. Gasteiger, H.A., Markovic, N.M., and Ross, P.N. (1995) Electrooxidation of CO and H2/CO mixtures on a well-characterized PtjSn electrode surface./. Phys. Chem., 99, 16757-16767. Wang, K., Gasteiger, H.A., Markovic, N.M., and Ross, P.M. (1996) On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt-Sn alloy versus Pt-Ru alloy surface. Electrochim. Acta, 41, 2587-2593. 

After the brief introduction to the modem methods of ab initio quantum chemistry, we will discuss specific applications. First of all, we will discuss some general aspects of the adsorption of atoms and molecules on electrochemical surfaces, including a discussion of the two different types of geometrical models that may be used to study surfaces, i. e. clusters and slabs, and how to model the effect of the electrode potential in an ab initio calculation. As a first application, the adsorption of halogens and halides on metal surfaces, a problem very central to interfacial electrochemistry, will be dealt with, followed by a section on the ab initio quantum chemical description of the adsorption of a paradigmatic probe molecule in both interfacial electrochemistry and surface science, namely carbon monoxide. Next we will discuss in detail an issue uniquely specific to electrochemistry, namely the effect of the electric field, i. e. the variable electrode potential, on the adsorption energy and vibrational properties of chemisorbed atoms and molecules. The potential-dependent adsorption of carbon monoxide will be discussed in a separate section, as this is a much studied system both in experimental electrochemistry and ab initio quantum electrochemistry. The interaction of water and water dissociation products with metal surfaces will be the next topic of interest. Finally, as a last... 

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