We present a quantum-mechanical study of silver decahedral nanoclusters and nanoparticles containing from 1 to 181 atoms in their static atomic configurations corresponding to the minimum of the ab initio computed total energies. Our thermodynamic analysis compares T = 0 K excess energies (without any excitations) obtained from a phenomenological approach, which mostly uses bulk-related properties, with excess energies from ab initio calculations of actual nanoclusters/nanoparticles. The phenomenological thermodynamic modeling employs (i) the bulk reference energy, (ii) surface energies obtained for infinite planar (bulk-related) surfaces and (iii) the bulk atomic volume. We show that it can predict the excess energy (per atom) of nanoclusters/nanoparticles containing as few as 7 atoms with the error lower than 3%. The only information related to the nanoclusters/nanoparticles of interest, which enters the phenomenological modeling, is the number of atoms in the nanocluster/nanoparticle, the shape and the crystallographic orientation(s) of facets. The agreement between both approaches is conditioned by computing the bulk-related properties with the same computational parameters as in the case of the nanoclusters/nanoparticles but, importantly, the phenomenological approach is much less computationally demanding. Our work thus indicates that it is possible to substantially reduce computational demands when computing excess energies of nanoclusters and nanoparticles by ab initio methods.

Central European Institute of Technology CEITEC IPM Institute of Physics of Materials Czech Academy of Sciences Žižkova 22 616 62 Brno Czech Republic

Central European Institute of Technology CEITEC MU Masaryk University Kamenice 753 5 625 00 Brno Czech Republic

Department of Chemistry Faculty of Science Masaryk University Kotlářská 2 611 37 Brno Czech Republic

Institute of Physics of Materials Czech Academy of Sciences Žižkova 22 616 62 Brno Czech Republic

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Best-Practice Aspects of Quantum-Computer Calculations: A Case Study of the Hydrogen Molecule

Editorial for the Special Issue on Computational Quantum Physics and Chemistry of Nanomaterials