123883 20241125101129.0 doi 10.3390/ijms24010870 sideral 132398 ART-2023-132398 eng Barrena Espés, Daniel Exploring the potential energy surface of Pt6 sub-nano clusters deposited over graphene 2023 Access copy available to the general public Unrestricted Catalytic systems based on sub-nanoclusters deposited over different supports are promising for very relevant chemical transformations such as many electrocatalytic processes as the ORR. These systems have been demonstrated to be very fluxional, as they are able to change shape and interconvert between each other either alone or in the presence of adsorbates. In addition, an accurate representation of their catalytic activity requires the consideration of ensemble effects and not a single structure alone. In this sense, a reliable theoretical methodology should assure an accurate and extensive exploration of the potential energy surface to include all the relevant structures and with correct relative energies. In this context, we applied DFT in conjunction with global optimization techniques to obtain and analyze the characteristics of the many local minima of Pt6 sub-nanoclusters over a carbon-based support (graphene)—a system with electrocatalytic relevance. We also analyzed the magnetism and the charge transfer between the clusters and the support and paid special attention to the dependence of dispersion effects on the ensemble characteristics. We found that the ensembles computed with and without dispersion corrections are qualitatively similar, especially for the lowest-in-energy clusters, which we attribute to a (mainly) covalent binding to the surface. However, there are some significant variations in the relative stability of some clusters, which would significantly affect their population in the ensemble composition. info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00 info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 4.9 2023 BIOCHEMISTRY & MOLECULAR BIOLOGY 66 / 313 = 0.211 2023 Q1 T1 CHEMISTRY, MULTIDISCIPLINARY 68 / 231 = 0.294 2023 Q2 T1 1.179 2023 Medicine (miscellaneous) 2023 Q1 Physical and Theoretical Chemistry 2023 Q1 Computer Science Applications 2023 Q1 Inorganic Chemistry 2023 Q1 Spectroscopy 2023 Q1 Organic Chemistry 2023 Q1 Molecular Biology 2023 Q2 Catalysis 2023 Q2 8.1 2023 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Boneta, Sergio Universidad de Zaragoza Polo, Victor Universidad de Zaragoza (orcid)0000-0001-5823-7965 Munárriz, Julen Universidad de Zaragoza (orcid)0000-0001-6089-6126 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 1002 060 Universidad de Zaragoza Dpto. Bioq.Biolog.Mol. Celular Área Bioquímica y Biolog.Mole. 24, 1 (2023), 870 [12 pp] Int. j. mol. sci. International Journal of Molecular Sciences 1661-6596 3728941 http://zaguan.unizar.es/record/123883/files/texto_completo.pdf Versión publicada 2649832 http://zaguan.unizar.es/record/123883/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:123883 articulos driver 2024-11-22-11:58:26 ARTICLE