Facile dissociation of CO on Fe{2 1 1}: Evidence from microcalorimetry and first-principles theory

Surface Science

Volumn 602, Issue 13, 2008, Pages 2325-2332

  Borthwick, David ^a   Fiorin, Vittorio ^a   Jenkins, Stephen J ^a   King, David A ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

Carbon monoxide; Density functional calculations; Heat of adsorption; Single crystal adsorption calorimetry; Stepped iron surfaces; Sticking

Indexed keywords

ADSORPTION; ATOMIC PHYSICS; ATOMS; CALORIMETERS; CHEMISORPTION; COBALT; COBALT ALLOYS; COBALT COMPOUNDS; IRON; METALLIZING; MICROFLUIDICS; PROBABILITY DENSITY FUNCTION; SINGLE CRYSTAL SURFACES; SOLID STATE PHYSICS; SPECTROSCOPIC ANALYSIS;

(1 1 0) SURFACE; ADSORPTION CALORIMETRY; FIRST-PRINCIPLES DENSITY FUNCTIONAL THEORY; FIRST-PRINCIPLES THEORY; METAL ATOMS; MICROCALORIMETRY; MOLECULAR ADSORPTION (MA); RED-SHIFTED; SECOND LAYER; STRETCHING FREQUENCIES;

DENSITY FUNCTIONAL THEORY;

EID: 45849133396     PISSN: 00396028     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.susc.2008.05.014     Document Type: Article

References (38)

1. Ge Q., Jenkins S.J., and King D.A. Chem. Phys. Lett. 327 (2000) 125
2. Jenkins S.J., Ge Q., and King D.A. Phys. Rev. B 64 (2001) 012413
3. Jenkins S.J., and King D.A. J. Am. Chem. Soc. 122 (2000) 10610
4. Jenkins S.J., and King D.A. Surf. Sci. 504 (2002) 138
5. Jenkins S.J., and King D.A. Surf. Sci. 529 (2003) 312
6. Pratt S.J., Jenkins S.J., and King D.A. Surf. Sci. 585 (2005) L159
7. Jenkins S.J., and Pratt S.J. Surf. Sci. Rep. 62 (2007) 373
8. Bernasek S.L. Annu. Rev. Phys. Chem. 44 (1993) 265
9. Jenkins S.J. In: Leszczynski J. (Ed). Computational Materials Science (2004), Elsevier, Amsterdam
10. Huo C.-F., Ren J., Li Y.-W., Wang J., and Jiao H. J. Catal. 249 (2007) 174
11. Sorescu D.C., Thompson D.L., Hurley M.M., and Chabalowski C.F. Phys. Rev. B 66 (2002) 035416
12. Bromfield T.C., Curulla Ferre D., and Niemantsverdriet J.W. Chem. Phys. Chem. 6 (2005) 254
13. Stibor A., Kresse G., Eichler A., and Hafner J. Surf. Sci. 507 (2002) 99
14. Jenkins S.J. Surf. Sci. 600 (2006) 1431
15. Monkhorst H.J., and Pack J.D. Phys. Rev. B 13 (1976) 5188
16. Vanderbilt D. Phys. Rev. B 41 (1990) 7892
17. Louie S.G., Froyen S., and Cohen M.L. Phys. Rev. B 26 (1982) 1738
18. Perdew J.P., Chevary J.A., Vosko S.H., Jackson K.A., Pederson M.R., Singh D.J., and Fiolhais C. Phys. Rev. B 46 (1992) 6671
19. Hammer B., Hansen L.B., and Norskov J.K. Phys. Rev. Lett. 59 (1999) 7413
20. Bader R.F.W. Atoms in Molecules: A Quantum Theory (1990), Oxford University Press, Oxford, UK
21. Borroni-Bird C.E., and King D.A. Rev. Sci. Instr. 62 (1991) 2177
22. Stuck A., Wartnaby C.E., Yeo Y.Y., Stuckless J.T., Al-Sarraf N., and King D.A. Surf. Sci. 349 (1996) 229
23. King D.A., and Wells M.G. Surf. Sci. 29 (1972) 454
24. Sokolov J., Shih H.D., Bardi U., Jona F., and Marcus P.M. Solid State Commun. 48 (1983) 739
25. Sokolov J., Jona F., and Marcus P.M. Solid State Commun. 49 (1984) 307
26. Nayak S.K., Nooijen M., Bernasek S.L., and Blaha P. J. Phys. Chem. B 105 (2001) 164
27. Moon D.W., Bernasek S.L., Dwyer D.J., and Gland J.L. J. Am. Chem. Soc. 107 (1985) 4363
28. Sokolov J., Jona F., and Marcus P.M. Eur. Phys. Lett. 1 (1986) 401
29. We neglect the possibility that CO may first diffuse to a metastable site prior to dissociation. Although possible in principle, and indeed observed in some calculations for other systems, the rationale for such a pathway is based upon the metastable geometry being somehow closer to the product state than is the molecular ground state geometry. Since the lowest-energy molecular geometry in the present system is also structurally closest to a plausible transition state (i.e. the molecule is strongly tilted and stretched) it seems highly improbable that any alternative metastable initial geometry (with a more vertical molecule and a shorter, stronger C-O bond) could be linked to a barrier low enough to compensate for the higher initial energy.
30. Karmazyn A., Fiorin V., and King D.A. Surf. Sci. 547 (2003) 184
31. Kisliuk P.J. Phys. Chem. Solids 3 (1957) 95
32. Brown W.A., Kose R., and King D.A. Chem. Rev. 98 (1998) 797
33. Kose R., Brown W.A., and King D.A. J. Phys. Chem. B 103 (1999) 8722
34. Karmazyn A.D., Fiorin V., Jenkins S.J., and King D.A. Surf. Sci. 538 (2003) 171
35. Moon D.W., Dwyer D.J., and Bernasek S.L. Surf. Sci. 163 (1985) 215
36. Benziger J.B., and Madix R.J. Surf. Sci. 94 (1980) 119
37. Jiang D.E., and Carter E.A. Surf. Sci. 570 (2004) 167
38. Jiang D.E., and Carter E.A. Phys. Rev. B 71 (2005) 045402