Ab initio study of magnesium surface properties with CRYSTAL program package

Saleev V.A., Shipilova A.V.

Samara National Research University


We have performed ab initio study of different magnesium surface properties based on density functional theory methods [1] in general gradient approximation (GGA) level with Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional [2]. Numerical calculations have been done with CRYSTAL14 program package [3] exploring modified Gaussian-type DZVP basis sets for magnesium and oxygen atoms from article [4]. Using super-cell approach we found magnesium surface energies in the range of 39 – 64 meV/ Å2 for different crystallographic planes with Miller’s indices (001), (100) and (110). The electron work functions found to be in the range 3.16-3.73 eV that is a little smaller of experimental value for (001) plane – 3.84 eV [5]. We have obtained good agreement with experimental data for calculated inter-layer distances for first three layers new the surface. Obtained values of oxygen adsorption energies are in good agreement with previous study with VASP program package [6], 4.9-5.1 eV per oxygen atom. We have found that energy shifts of 2p electron in magnesium atoms new surface are in range 0.1-1.0 eV depending on oxygen density. [1] P. Hohenberg and W. Kohn, Phys. Rev. 136 (1964) B864; [2] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865; [3] R. Dovesi, R. Orlando, B. Civalleri, C. Roetti, V.R. Saunders, C.M. Zicovich-Wilson, Z. Kristallogr., 220 (2005) 571; [4] M.F. Peintinger, D. V. Oliveira and T. Bredow, J. Comput. Chem., 2013, 34, 451; [5] H.B. Michaelson, J. Appl. Phys. 48, 4729 (1977); [6] E.Schroder, R. Fasel, A. Kiejna, Phys. Rev. B 69,193405 (2004).