A Semiempirical Method to Detect and Correct DFT-Based Gas-Phase Errors and Its Application in Electrocatalysis

ACS Catalysis, vol. 10, pp. 6900–6907

Abstract

Abstract Computational models of adsorption at metal surfaces are often based on DFT and make use of the generalized gradient approximation. This likely implies the presence of sizable errors in the gas-phase energetics. Here, we take a step closer toward chemical accuracy with a semiempirical method to correct the gas-phase energetics of PBE, PW91, RPBE, and BEEF-vdW exchange–correlation functionals. The proposed two-step method is tested on a data set of 27 gas-phase molecules belonging to the carbon cycle: first, the errors are pinpointed based on formation energies, and second, the respective corrections are sequentially applied to ensure the progressive lowering of the data set’s mean and maximum errors. We illustrate the benefits of the method in electrocatalysis by a substantial improvement of the calculated equilibrium and onset potentials for CO2 reduction to CO on Au, Ag, and Cu electrodes. This suggests that fast and systematic gas-phase corrections can be devised to augment the predictive power of computational catalysis models.

Authors 6

1. Laura P. Granda‐Marulanda Aachen

   Leiden University · Universitat de Barcelona

   Affiliation as printed

   Leiden University , , PO Box 9502, ,

   Universitat de Barcelona , , Martı́ i Franquès 1 , ,

   Departament de Ciència de Materials i Quı́mica Fı́sica & Institut de Quı́mica Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martı́ i Franquès 1, Barcelona 08028, Spain

   Leiden Institute of Chemistry, Leiden University, PO Box 9502, Leiden 2300RA, The Netherlands

2. Alejandra Rendón-Calle

   Universitat de Barcelona · Universidad EAFIT

   Affiliation as printed

   Universidad EAFIT , , Carrera 49 #7 sur 50 , ,

   Universitat de Barcelona , , Martı́ i Franquès 1 , ,

   Departament de Ciència de Materials i Quı́mica Fı́sica & Institut de Quı́mica Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martı́ i Franquès 1, Barcelona 08028, Spain

   Departamento de Ingenierı́a de Procesos, Universidad EAFIT, Carrera 49 #7 sur 50, Medellín 050022, Colombia

3. Santiago Builes

   Universidad EAFIT

   Affiliation as printed

   Universidad EAFIT , , Carrera 49 #7 sur 50 , ,

   Departamento de Ingenierı́a de Procesos, Universidad EAFIT, Carrera 49 #7 sur 50, Medellín 050022, Colombia

4. Francesc Illas

   Universitat de Barcelona

   Affiliation as printed

   Universitat de Barcelona , , Martı́ i Franquès 1 , ,

   Departament de Ciència de Materials i Quı́mica Fı́sica & Institut de Quı́mica Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martı́ i Franquès 1, Barcelona 08028, Spain

5. Marc T. M. Koper corresponding Aachen

   Leiden University

   Affiliation as printed

   Leiden University , , PO Box 9502, ,

   Leiden Institute of Chemistry, Leiden University, PO Box 9502, Leiden 2300RA, The Netherlands

6. Federico Calle‐Vallejo corresponding

   Universitat de Barcelona

   Affiliation as printed

   Universitat de Barcelona , , Martı́ i Franquès 1 , ,

   Departament de Ciència de Materials i Quı́mica Fı́sica & Institut de Quı́mica Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martı́ i Franquès 1, Barcelona 08028, Spain