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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Transition-metal 13-atom clusters assessed with solid and surface-biased functionals
Maurício J Piotrowski1, Paulo Piquini, Mariana M Odashima
1Departamento de Física, Universidade Federal de Santa Maria, Santa Maria, RS, Brazil. mauriciomjp@gmail.com
The Journal of Chemical Physics
|April 12, 2011
Summary
Density-functional theory studies reveal that transition metal clusters (TM(13)) unexpectedly favor open double simple-cubic (DSC) structures. Various exchange-correlation functionals confirm this DSC configuration as the lowest energy state for these clusters.
Area of Science:
- Computational materials science
- Quantum chemistry
- Condensed matter physics
Background:
- Bulk transition metals like Ruthenium (Ru), Rhodium (Rh), Osmium (Os), and Iridium (Ir) typically form compact structures (FCC, HCP).
- Previous first-principles studies suggested unexpected open double simple-cubic (DSC) structures for TM(13) clusters.
Purpose of the Study:
- Investigate the influence of different exchange-correlation (xc) functionals on the lowest-energy structure of TM(13) clusters.
- Determine if xc functional choice affects the stability of the reported DSC structures.
Main Methods:
- Employed the projected augmented wave (PAW) method within density-functional theory (DFT).
- Utilized various local and semilocal xc functionals: local-density approximation (LDA), PBE, PBEsol, and AM05.
- Calculated relative total energies and total magnetic moments for different cluster structures.
Main Results:
- All tested xc functionals (LDA, PBE, PBEsol, AM05) consistently predict the DSC arrangement as the lowest-energy structure for Ru(13), Rh(13), Os(13), and Ir(13) clusters.
- Good agreement was observed in relative total energies, even for structures with small energy differences (around 0.10 eV).
- The employed xc functionals yielded identical total magnetic moments for a given structure, indicating robustness against minor bond length variations.
Conclusions:
- The DSC configuration is robustly identified as the ground state structure for TM(13) clusters across various common xc functionals.
- Differences among LDA, PBE, PBEsol, and AM05 functionals are insufficient to produce qualitatively different structural or magnetic outcomes for these specific TM(13) systems.
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