Mohan, Ojus Trinh, Quang Thang Banerjee, Arghya Mushrif, Samir H. Predicting CO<sub>2</sub> adsorption and reactivity on transition metal surfaces using popular density functional theory methods <p>In this work, with Ni (110) as a model catalyst surface and CO<sub>2</sub> as an adsorbate, a performance study of Density Functional Theory methods (functionals) is performed. CO being a possible intermediate in CO<sub>2</sub> conversion reactions, binding energies of both, CO<sub>2</sub> and CO, are calculated on the Ni surface and are compared with experimental data. OptPBE-vdW functional correctly predicts CO<sub>2</sub> binding energy on Ni (−62 kJ/mol), whereas CO binding energy is correctly predicted by the rPBE-vdW functional (−138 kJ/mol). The difference in computed adsorption energies by different functionals is attributed to the calculation of gas phase CO<sub>2</sub>. Three alternate reaction systems based on a different number of C=O double bonds present in the gas phase molecule are considered to replace CO<sub>2</sub>. The error in computed adsorption energy is directly proportional to the number of C=O double bonds present in the gas phase molecule. Additionally, both functionals predict similar carbon–oxygen activation barrier (40 kJ/mol) and equivalent C1s shifts for probe species (−2.6 eV for CCH<sub>3</sub> and +1.5 eV CO<sub>3</sub><sup>−</sup>), with respect to adsorbed CO<sub>2</sub>. Thus, by including a correction factor of 28 kJ/mol for the computed CO<sub>2</sub> gas phase energy, we suggest using rPBE-vdW functional to investigate CO<sub>2</sub> conversion reactions on different metals.</p> Density functional theory;carbon dioxide adsorption;DFT–XPS;DFT accuracy 2019-06-26
    https://tandf.figshare.com/articles/journal_contribution/Predicting_CO_sub_2_sub_adsorption_and_reactivity_on_transition_metal_surfaces_using_popular_density_functional_theory_methods/8325593
10.6084/m9.figshare.8325593.v1