Effect of the exchange-correlation potential and of surface relaxation on the description of the H2O dissociation on Cu(111)

resumo

The role of the exchange-correlation density functional (PBE, PW91, RevPBE) and of surface relaxation in the determination of the adsorption energies, reaction energy barriers, and reaction rate constants has been analyzed taking water dissociation on Cu(111) surface as a test case. The PBE and PW91 functionals yield similar adsorption geometries and, adsorption and activation energies, but differ significantly from RevPBE results. For each of the functionals tested, surface relaxation was found to have only a minor effect on the calculated (co)adsorption geometries and (co)adsorption energies. The calculated energy barriers for water dissociation are more affected by the functional used, especially in the case of the RevPBE, with obvious implications on the calculated energy barriers and derived reaction rate constants. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3149851]

palavras-chave

GAS SHIFT REACTION; GENERALIZED GRADIENT APPROXIMATION; TOTAL-ENERGY CALCULATIONS; AUGMENTED-WAVE METHOD; METHANOL SYNTHESIS; TRANSITION-METALS; WATER-ADSORPTION; CU(HKL) SURFACES; BASIS-SET; CATALYSTS

categoria

Chemistry; Physics

autores

Fajin, JLC; Illas, F; Gomes, JRB

nossos autores

agradecimentos

Financial support from FEDER, Portuguese Fundacao para a Ciencia e Tecnologia (FCT), Conselho de Reitores das Universidades Portuguesas (CRUP), and Spanish Ministerio de Ciencia e Innovacion (MICCIN), through Grant Nos. Programa Ciencia 2007, Accao E-43/08, FIS2008-02238, and HP2007-0042, is fully acknowledged. J. L. C. F. thanks FCT for a post-doctoral grant (Grant No. SFRH/BPD/27167/2006)

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