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Theoretical prediction of low-energy photoelectron spectra of AlnNi− clusters (n = 1–13)

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Abstract

Context

Mixed-metal clusters have long been studied because of their peculiar properties and how they change with cluster size, composition, and charge state and their potential roles in catalysis. The characterization of these clusters is therefore a very important issue. One of the main experimental tools for characterizing their electronic structure is photoelectron spectroscopy. Theoretical computation completes the task by fully determining the structural properties and matching the theoretical predictions to the measured spectra. We present density functional theory computations of the structural, magnetic, and electronic properties of negatively charged mixed AlnNi- clusters with up to 13 Al atoms. The lowest energy structures of the anionic clusters with up to 7 atoms are also found to be low-energy isomers of the neutral counterparts found in the literature. The 13-atom cluster is found to be a quartet and a perfect icosahedron. The predicted photoelectron spectra are also presented and can be used to interpret future experimental data. We also presented indicators that can be used to determine the potential of these systems for single-atom catalysis. These indicators point to smaller clusters to be more reactive as the gap between the Fermi energy and the center of the d-band increases with cluster size and that Ni occupies an internal site for n = 11–13. We speculate that reactivity can be enhanced if one adds an additional Ni atom.

Methods

The DFT calculations were performed using the Becke exchange and Perdew-Wang/91 correlation functionals (BPW91), a DFT-optimized all-electron basis set for the aluminum atom, and the Stuttgart small core pseudopotential for the Ni atom. All of the computations used the Gaussian 03 software.

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Data availability

All data underlying the results are available as part of the article and no additional source data are required.

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Acknowledgements

This work was supported by the Northeastern Illinois University Department of Physics and Astronomy.

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  1. Department of Physics, Northeastern Illinois University, Chicago, IL, 60625, USA

    Paulo H. Acioli

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  1. Paulo H. Acioli
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Paulo H Acioli performed all the calculations, prepared all the tables and figures and the analysis in the submitted manuscript.

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Correspondence to Paulo H. Acioli.

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Acioli, P.H. Theoretical prediction of low-energy photoelectron spectra of AlnNi− clusters (n = 1–13). J Mol Model 30, 155 (2024). https://doi.org/10.1007/s00894-024-05944-x

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