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

• Tipo: Artigo em Revista Científica Internacional
• Data: 2016

Autores

Jose L C Fajin (Autor) FCUP; Vines, F (Autor) Outra; Natalia N D S Cordeiro (Autor) FCUP; Illas, F (Autor) Outra; Gomes, JRB (Autor) Outra

Revista

Título: Journal of Chemical Theory and Computation

Vol. 12

Páginas: 2121-2126

ISSN: 1549-9618

Editora: American Chemical Society

Indexação

ISI Web of Knowledge - 18 Citações

Scopus - 18 Citações

Outras Informações

ID Authenticus: P-00K-FJY

DOI: 10.1021/acs.jctc.6b00168

Abstract (EN): 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.

Idioma: Inglês

Tipo (Avaliação Docente): Científica

Nº de páginas: 6