Comparison of the full-potential and frozen-core approximation approaches to density-functional calculations of surfaces

We scrutinize the accuracy of the pseudopotential approximation in density-functional theory calculations of surfaces by systematically comparing to results obtained within a full-potential setup. As model system we choose the CO oxidation at a RuO2110 surface and focus in particular on the adsorbate binding energies and reaction barriers as target quantities for the comparison. Rather surprisingly, the major reason for discrepancy does not result from the neglected semicore state relaxation in the frozen-core approximation, but from an inadequate description of the local part of the Ru pseudopotential, responsible for the scattering of f-like waves. Tiny, seemingly irrelevant, imprecisions appearing in these properties can have a noticeable influence on the surface energetics. At least for the present example, we obtain excellent agreement between both approaches, if the pseudopotential describes these scattering properties accurately.

[1]  M. V. Ganduglia-Pirovano,et al.  Atomistic description of oxide formation on metal surfaces: the example of ruthenium , 2002 .

[2]  G. Ertl,et al.  The oxidation of CO on RuO2(110) at room temperature , 2001 .

[3]  A. Seitsonen,et al.  CO adsorption on the reduced RuO2(110) surface: Energetics and structure , 2001 .

[4]  H. Over,et al.  Catalytic CO oxidation over ruthenium––bridging the pressure gap , 2003 .

[5]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[6]  G. Ertl,et al.  Identification of RuO2 as the active phase in CO oxidation on oxygen-rich ruthenium surfaces , 2000 .

[7]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[8]  Georg Kresse,et al.  The Perdew-Burke-Ernzerhof exchange-correlation functional applied to the G2-1 test set using a plane-wave basis set. , 2005, The Journal of chemical physics.

[9]  D. Vanderbilt,et al.  Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. , 1990, Physical review. B, Condensed matter.

[10]  Scheffler,et al.  Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111). , 1992, Physical review. B, Condensed matter.

[11]  A. Seitsonen,et al.  Adsorption characteristics of CO and N2 on RuO2(110) , 2001 .

[12]  Matthias Scheffler,et al.  Composition, structure, and stability of RuO2(110) as a function of oxygen pressure , 2001 .

[13]  M. Scheffler,et al.  Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory , 1998, cond-mat/9807418.

[14]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[15]  G. Ertl,et al.  The kinetics of CO oxidation on RuO2(110): Bridging the pressure gap , 2002 .

[16]  Georg Kresse,et al.  Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements , 1994 .

[17]  G. Ertl,et al.  CO OXIDATION REACTION OVER OXYGEN-RICH RU(0001) SURFACES , 1997 .

[18]  M. Gillan.  Calculation of the vacancy formation energy in aluminium , 1989 .

[19]  M. Scheffler,et al.  Composition and structure of the RuO2(110) surface in an O2 and CO environment: Implications for the catalytic formation of CO2 , 2003, cond-mat/0301602.

[20]  David J. Singh,et al.  An alternative way of linearizing the augmented-plane-wave method , 2000 .

[21]  Varga,et al.  Atomic-scale structure and catalytic reactivity of the RuO(2)(110) surface , 2000, Science.

[22]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[23]  Matthias Scheffler,et al.  First-principles atomistic thermodynamics for oxidation catalysis: surface phase diagrams and catalytically interesting regions. , 2003, Physical review letters.

[24]  Catherine Stampfl,et al.  Density-functional calculations for III-V nitrides using the local-density approximation and the generalized gradient approximation , 1999 .

[25]  A. Alavi,et al.  Mechanism for the high reactivity of CO oxidation on a ruthenium–oxide , 2001 .

[26]  Kieffer.  Mechanical degradation and viscous dissipation in B2O3. , 1994, Physical review. B, Condensed matter.

[27]  Xue-qing Gong,et al.  A systematic study of CO oxidation on metals and metal oxides: density functional theory calculations. , 2004, Journal of the American Chemical Society.

[28]  Paxton,et al.  High-precision sampling for Brillouin-zone integration in metals. , 1989, Physical review. B, Condensed matter.

[29]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[30]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[31]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[32]  Elisabeth Sjöstedt,et al.  Efficient linearization of the augmented plane-wave method , 2001 .

[33]  K. Schwarz,et al.  Electronic structure calculations of solids using the WIEN2k package for material sciences , 2002 .

[34]  G. Ertl,et al.  Characterization of Various Oxygen Species on an Oxide Surface: RuO2(110) † , 2001 .

[35]  Chemical hardness, linear response, and pseudopotential transferability. , 1995, Physical review. B, Condensed matter.

[36]  Teter.  Additional condition for transferability in pseudopotentials. , 1993, Physical review. B, Condensed matter.

[37]  Daan Frenkel,et al.  The steady state of heterogeneous catalysis, studied by first-principles statistical mechanics. , 2004, Physical review letters.