@article{b9de988206824dd59c24b4bd987fa3d2,
title = "Calculation of the electronic structure of ethylene bonded to diatomic nickel and correlation with Ni-C2 H2 photo-emission data",
abstract = "The electronic structure of a model {"}surface complex{"} consisting of a Ni-diatom and an ethylene molecule has been calculated using the SCF-Xα scattered-wave method. Comparison of calculated π-orbital bonding shifts with recent photoemission spectra for chemisorption of ethylene of nickel favours a π-bonded over a σ-diadsorbed complex. Charge distributions of various molecular orbitals indicate that the C - C double-bond is weakened more for the latter molecular arrangement suggesting such a complex as a likely intermediate in heterogeneous reactions.",
author = "N. R{\"o}sch and Rhodin, {T. N.}",
note = "Funding Information: tion the bonding of hydrocarbons to a metallic diatom. implemented with the SCF-Xu-SW method can yield unique information on We thank Drs. J. E. Demuth and D. E. Eastman for making their results available before publication. We are particularly grateful to Prof. K. H. Johnson for providing us with the Xa-SW computer programmes and helpful advice in the use of the method. 58-B34 BONDING OF ETHYLENE TO DIATOMIC NICKEL Useful discussions with Dr. R. H. Paulsen are also acknowledged. The continued in- terest and support of Prof. Roald Hoffmann in this work is sincerely appreciated. One of us (N. R.) is also grateful to the Deutsche Forschungsgemeinschaft for a sti- pend. J. E. Demuth and D. E. Eastman, Phys. Rev. Letters, 1974, 32, 1123. E. W. Plummer et al., private communication. J. C. Slater and K. H. Johnson, Phys. Reu. B, 1972,5, 844. N. Rosch, R. P. Messmer and K. H. Johnson, J. Arner. Chem. SOC., 1974,96, 3855. T. B. Grimley, in Molecular Processes on Solid Surfaces, ed. E. Drauglis, R. D. Gretz and R. 1. J d e (McGraw-Hill, New York, 1969), p. 299. K. H. Johnson and R. P. Messmer, J. Vac. Sci. Tech., 1974, to be published. J. Chem. SOC., 1953,2939. G. C. Bond, Disc. Faraday SOC., 1966,41,200. G. C. Bond, CataZysis by Metals (Academic Press, New York, 1962), p. 234. (Academic Press, New York, 1973), vol. 23, p. 91. B. A. Morrow and N. Sheppard, Proc. Roy. SOC. A, 1969,311,391. ' (a) M. J. S . Dewar, Bull. SOC. Chim. France, 1951,18, C79 ; (b) J. Chatt and L. A. Duncanson, lo (a) G. I. Jenkins and E. K. Rideal, J. Chem. Soc., 1955, 2491 ; (6) J. H. Sinfelt, Ado. CatalysiJ I2 N. Rosch, W. G. Klemperer and K. H. Johnson, Chern. Phys. Letters, 1973, 23, 149. l3 K. Schwarz, Phys. Rev. B, 1972, 5, 2466. l4 We thank Dr. R. Paulson for kindly providing us with these results. J. M. Baker and D. E. Eastman, J. Vac. Sci. Tech., 1973, 10, 223. l6 W. C. Hamilton, K. A. Klandermann and R. Spratley, Acta Cryst. A, 1969, 25, S172. Funding Information: As a model for the “surface complex” we choose a Ni-diatom with a bond length of 2.492A (4.709 a.u.) equal to the nearest neighbour distance in bulk Ni and an ethylene molecule with equilibrium geometry. Corresponding to the two possible bonding schemes, two different geometrical arrangements have been studied. In the complex representing the a-diadsorbed ethylene, the Ni-Ni bond has been taken parallel to the plane of the ethylene molecule ; in the n-complex the N i N i bond was * Supported by NSF Grant GH-31909, and by the Advanced Research Projects Agency through the Cornell Materials Science Centre. -f permanent address : Lehrstuhl fur Theoretische Chemie, Technische Universitat, Miinchen. ",
year = "1974",
doi = "10.1039/DC9745800028",
language = "English",
volume = "58",
pages = "28--34",
journal = "Faraday Discussions of the Chemical Society",
issn = "0301-7249",
}