Effect of the Exchange-Correlation Potential on the Transferability of Brønsted–Evans–Polanyi Relationships in Heterogeneous Catalysis

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• 作者：José L. C. Fajín ; Francesc Viñes ; M. Natália D. S. Cordeiro ; Francesc Illas ; José R. B. Gomes
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：May 10, 2016
• 年：2016
• 卷：12
• 期：5
• 页码：2121-2126
• 全文大小：332K
• 年卷期：0
• ISSN：1549-9626

文摘

As more and more accurate density functional methods emerge, the transferability of Brønsted–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.