First-Principles Calculation of Water Molecules with Adsorbed Ions on the Fe(001) Surface

Abstract:

The behavior of water molecules with sulfate on the Fe(001) surface has been investigated using a first-principles method based on density-functional theory (DFT) with numerical atomic orbitals as basis functions for the description of valence electrons and nonlocal pseudopotentials for the atomic core. We present results for the adsorption structure and the bonding nature as caused by the adsorption-induced variations in the electron density and the projected density of states. We have found that the structure of absorbed sulfate depends on the coverage of water molecule on the surface. Analysis of electrostatic potential at an aqueous metal interface provides an appropriate framework to understand complicated potential structures. The mechanism of proton transfer through dissociative adsorption and hydrogen bonding of water molecules has been obtained from calculated results.

• Periodical: Materials Science Forum (Volumes 654-656)
• Pages: 1662-1665
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.654-656.1662
• Online since: June 2010
• Authors: Norio Nunomura, Satoshi Sunada
• Keywords: Density Functional Calculation, Iron Surface, Molecular Dynamic (MD), Sulfate, Water

References

[1] M.A. Henderson: Surf. Sci. Rep. Vol. 46 (2002), p.5.

[2] A. Hodgson and S. Haq: Surf. Sci. Rep. Vol. 64 (2009), p.381.

[3] T. Kumagai, M. Kaizu, S. Hatta, H. Okuyama, T. Aruga, I. Hamada, Y. Morikawa: Phys. Rev. Lett. Vol. 100 (2008), p.166101.

DOI: 10.1103/physrevlett.100.166101

[4] T. Schiros, S. Haq, H. Ogasawara, O. Takahashi, H. Ostrom, K. Andersson, L.G.M. Petterson, A. Hodgson, and A. Nilsson: Chem. Phys. Lett. Vol. 429 (2006), p.415.

[5] M. Ito and M. Yamazaki: Phys. Chem. Chem. Phys. Vol. 8 (2006), p.3623.

[6] J.W. Halley and D. Price: Phys. Rev. B Vol. 35 (1986), p.9095.

[7] S. Izvekov and G.A. Voth: J. Chem. Phys. Vol. 115 (2001), p.7196.

[8] C.D. Taylor, S.A. Wasileski, J-S. Filhol and M. Neurock: Phys. Rev. B Vol. 73 (2006), p.165402.

[9] M. Otani, I. Hamada, O. Sugino, Y. Morikawa, Y. Okamoto and T. Ikeshoji: J. Phys. Soc. Jpn. Vol. 77 (2008), p.024802.

DOI: 10.1143/jpsj.77.024802

[10] http: /www. icmab. es/siesta.

[11] N. Troullier and J.L. Martins: Phys. Rev. B Vol. 43 (1991), p. (1993).

[12] J.P. Perdew, K. Burke and M. Ernzehof: Phys. Rev. Lett. Vol. 77 (1996), p.3865.

[13] H. J. Monkhorst and J. D. Pack: Phys. Rev. B Vol. 13 (1976), p.5188.

[14] S. Nose: J. Chem. Phys. Vol. 81 (1984), p.511.

[15] E.M. Patrito, P.P. Olivera and H. Sellers: Surf. Sci. Vol. 380 (1997), p.264.