Fajín José L C, Viñes Francesc, D S Cordeiro M Natália, Illas Francesc, Gomes José R B
LAQV@REQUIMTE, Faculdade de Ciências, Universidade do Porto , P-4169-007 Porto, Portugal.
Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona , c/Martí i Franquès 1, 08028 Barcelona, Spain.
J Chem Theory Comput. 2016 May 10;12(5):2121-6. doi: 10.1021/acs.jctc.6b00168. Epub 2016 Apr 29.
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.
随着越来越精确的密度泛函方法出现，用先前模型得到的布朗斯特-埃文斯-波兰尼（BEP）关系的可转移性是一个悬而未决的问题。在这项工作中，分析了从基于不同密度泛函理论的计算得出的BEP关系，以回答这个问题。特别地，选择将金属表面上发生的O-H键断裂反应的活化能与反应产物的吸附能联系起来的BEP关系作为案例研究。这些关系是用广泛使用的佩德韦-王（PW91）广义梯度近似（GGA）交换相关泛函以及更精确的meta-GGA陶-佩德韦-斯塔罗沃罗夫-斯库塞里亚（TPSS）泛函得到的。我们提供了令人信服的证据，表明从PW91和TPSS泛函得出的BEP关系基本一致。这一发现验证了先前发表的BEP关系，并表明反应活化能垒可以通过在计算要求较低的GGA水平上确定能量反应描述符值来获得；这是在未来旨在通过计算设计具有改进特性的催化剂的研究中要考虑的一个重要方面。
