resumo
As more and more accurate density functional methods emerge, the transferability of Bronsted-Evans-Polanyi (BEP) relationships obtained with previous models is an open question. In this work, BEP relationships derived from different density functional theory based calculations are analyzed to answer this question. In particular, BEP relationships linking the activation energy of O-H bond breaking reactions taking place on metallic surfaces with the adsorption energy of the reaction products are chosen as a case study. These relationships are obtained with the widely used Perdew-Wang (PW91) generalized gradient approximation (GGA) exchange-correlation functional and with the more accurate meta-GGA Tao-Perdew Staroverov-Scuseria (TPSS) one. We provide compelling evidence that BEP relationships derived from PW91 and TPSS functionals are essentially coincidental. This finding validates previously published BEP relationships and indicates that the reaction activation energy barrier can be obtained by the determination of the energy reaction descriptor value at the less computationally demanding GGA level; an important aspect to consider in future studies aimed at the computational design of catalysts :with improved characteristics.
palavras-chave
GENERALIZED GRADIENT APPROXIMATION; TRANSITION-METAL SURFACES; DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; LEVEL BINDING-ENERGIES; AUGMENTED-WAVE METHOD; MAIN-GROUP ELEMENTS; BROAD ACCURACY; BASIS-SET; MOLECULES
categoria
Chemistry; Physics
autores
Fajin, JLC; Vines, F; Cordeiro, MNDS; Illas, F; Gomes, JRB
nossos autores
José R. B. Gomes
Investigador Principalagradecimentos
This work was developed within the scope of the projects CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013), LAQV@REQUIMTE (UID/QUI/50006/2013), and CODE CAT (PTDC/QUI-QUI/117439/2010-FEDER-020977), financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. J.L.C.F. and J.R.B.G. acknowledge FCT for the grant SFRH/BPD/64566/2009 cofinanced by the Programa Operacional Potencial Humano (POPH)/Fundo Social Europeu (FSE) and Quadro de Referencia Estrategico Nacional 2009-2013 do Governo da Republica Portuguesa, and for the Programme Investigador FCT, respectively. The research carried out at the Universitat de Barcelona was supported by the Spanish MINECO Grant CTQ2015-64618-R and, in part, by Generalitat de Catalunya (Grants 2014SGR97 and XRQTC). F.V. thanks the MINECO for a postdoctoral Ramon y Cajal (RyC) Research Contract (RYC-2012-10129).