Molecular chemisorption as the theoretically preferred pathway for water adsorption on ideal rutile TiO2(110)

Physical Review Letters

Volumn 93, Issue 8, 2004, Pages

  Harris, Leonard A ^a,b   Quong, Andrew A ^b,c  

^a Department of Obstetrics Gynecology   (United States)

^b LAWRENCE LIVERMORE NATIONAL LABORATORY   (United States)

^c GEORGETOWN UNIVERSITY SCHOOL OF MEDICINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADSORPTION; COMPUTER SIMULATION; DISSOCIATION; INTERFACIAL ENERGY; MONOLAYERS; RELAXATION PROCESSES; SURFACE STRUCTURE; TITANIUM DIOXIDE;

IONIC RELAXATION; MOLECULAR STATE; PERIODIC DENSITY FUNCTIONS; WATER CHEMISTRY;

CHEMISORPTION;

EID: 19544380223     PISSN: 00319007     EISSN: None     Source Type: Journal    
DOI: 10.1103/PhysRevLett.93.086105     Document Type: Article

References (37)

1. U. Diebold, Surf. Sci. Rep. 48, 53 (2003).
2. M. A. Henderson, Surf. Sci. Rep. 46, 1 (2002).
3. F. H. Jones, Surf. Sci. Rep. 42, 75 (2001).
4. R. L. Kurtz, R. Stockbauer, T. E. Madey, E. Román, and J. L. de Segovia, Surf. Sci. 218, 178 (1989).
5. M. B. Hugenschmidt, L. Gamble, and C. T. Campbell, Surf. Sci. 302, 329 (1994).
6. M. A. Henderson, Surf. Sci. 355, 151 (1996).
7. M. A. Henderson, Langmuir 12, 5093 (1996).
8. D. Brinkley et al., Surf. Sci. 395, 292 (1998).
9. I. M. Brookes, C. A. Muryn, and G. Thornton, Phys. Rev. Lett. 87, 266103 (2001).
10. R. Schaub et al., Phys. Rev. Lett. 87, 266104 (2001).
11. S. Krischok et al., Surf. Sci. 495, 8 (2001).
12. M. Menetrey, A. Markovits, and C. Minot, Surf. Sci. 524, 49 (2003).
13. J. Goniakowski and M. J. Gillan, Surf. Sci. 350, 145 (1996).
14. P. J. D. Lindan, N. M. Harrison, J. M. Holender, and M. J. Gillan, Chem. Phys. Lett. 261, 246 (1996).
15. P. J. D. Lindan, N. M. Harrison, and M. J. Gillan, Phys. Rev. Lett. 80, 762 (1998).
16. C. Zhang and P. J. D. Lindan, J. Chem. Phys. 118, 4620 (2003).
17. S. P. Bates, G. Kresse, and M. J. Gillan, Surf. Sci. 409, 336 (1998).
18. E. V. Stefanovich and T. N. Truong, Chem. Phys. Lett. 299, 623 (1999).
19. W. Langel, Surf. Sci. 496, 141 (2002).
20. G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993); G. Kresse and J. Furthmüller, ibid. 54, 11 169 (1996); Comput. Mater. Sci. 6, 15 (1996).
21. G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993); G. Kresse and J. Furthmüller, ibid. 54, 11 169 (1996); Comput. Mater. Sci. 6, 15 (1996).
22. G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993); G. Kresse and J. Furthmüller, ibid. 54, 11 169 (1996); Comput. Mater. Sci. 6, 15 (1996).
23. D. Vanderbilt, Phys. Rev. B 41, 7892 (1990).
24. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13 244 (1992); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, ibid. 46, 6671 (1992).
25. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13 244 (1992); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, ibid. 46, 6671 (1992).
26. H. J. Monkhorst and J. D. Pack, Phys. Rev. B 13, 5188 (1976).
27. The adsorbate reference states were two-dimensional sheets of molecules, accounting for the proximity of the adsorbates, not isolated water molecules.
28. 2-O layers comprising the computational slab.
29. 2(110) surfaces.
30. S. P. Bates, G. Kresse, and M. J. Gillan, Surf. Sci. 385, 386 (1997).
31. Although the FPMD simulations in [15,16] were performed on three-layer slabs, the adsorption energies reported were for five- and seven-layer slabs, respectively. In [15] these calculations showed mixed adsorption to be most favorable at ML coverage while in [16] a stable molecular state could not be identified via FPMD. Slab thickness effects may thus explain the result in [16] but not those in [15]. The use of a different basis set and fewer k points in [15] may, however. Nonetheless, the observations of mixed adsorption in FPMD in [15,16] are consistent with our three-layer results.
32. D. Vogtenhuber, R. Podloucky, and J. Redinger, Surf. Sci. 402-404, 798 (1998).
33. Again, slab thickness effects cannot explain why inline dissociative was favored at 1/2 ML coverage on a seven-layer slab in [16]. The FPMD observations in [14,16] are, nonetheless, consistent with our three-layer results.
34. Although here the difference between molecular and inline dissociative is within the error bars of the calculation. Nevertheless, the clear preference for molecular adsorption is apparent via the "25% rule."
35. In [16], and confirmed by our own unpublished results, it was shown that adsorbate asymmetries in the [001] direction minimally affect the adsorption energetics. That interactions in [110] also appear to be minimal suggests, therefore, that asymmetry effects are unlikely to alter the relative energetics between modes. The results presented here should thus be generally representative of all possible ML/sub-ML adsorption states.
36. Lindan et al. [15] also reported larger adsorption energies at higher coverages, but in comparing to the TPD results they incorrectly associated the larger values with the higher temperature (hence, lower coverage) part of the feature, and vice versa
37. Although adsorbate asymmetries are unlikely to affect the relative energetics [32], they may contribute to the broadness of the first-layer TPD feature [5,6,8].