Anion photoelectron spectroscopy and density functional theory study of TM2Sin− (TM = V, Cr; n = 14–20) clusters

We investigated the structural evolution and electronic properties of medium-sized silicon cluster anions doped with two transition metal atoms, TM2Sin− (TM = V, Cr; n = 14–20), by using mass-selective anion photoelectron spectroscopy combined with density functional theory (DFT) calculations. Putat...

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Published in:Physical chemistry chemical physics : PCCP 2022-08, Vol.24 (30), p.18321-18330
Main Authors: Wang, Kai, Guang-Jia Yin, Ze-Zhao Jia, Lin, Miao, Moro, Ramiro, Bernd von Issendorff, Ma, Lei
Format: Article
Language:English
Subjects:
Anions
Atomic properties
Chromium
Clusters
Density functional theory
Electronic properties
Fullerenes
Genetic algorithms
Magnetic moments
Mathematical analysis
Photoelectron spectroscopy
Photoelectrons
Silicon
Spectrum analysis
Transition metals
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Summary:We investigated the structural evolution and electronic properties of medium-sized silicon cluster anions doped with two transition metal atoms, TM2Sin− (TM = V, Cr; n = 14–20), by using mass-selective anion photoelectron spectroscopy combined with density functional theory (DFT) calculations. Putative ground state structures of these clusters were obtained by using a genetic algorithm coupled with the DFT calculations. It was found that the two TM atoms tend to form a TM–TM bond, which – except for V2Si19− – is shorter than the nearest neighbour distance in the crystalline state of the respective metals. The V2Sin− clusters with n = 14 to 17 exhibit structures based on a silicon hexagonal antiprism, while the larger ones exhibit more fullerene-like cage structures. Cr2Sin− clusters follow the same trend, although with a silicon hexagonal prism structure for n = 14 and 15, and the transition to fullerene-like structures occurring at n = 17. Among these clusters, TM2Si18− have the largest average binding energy and second order differences in energy, therefore the highest relative stability. All of the clusters possess total magnetic moment of 1 μB, but with very different contributions from the doped TM atoms. Especially in the Cr doped clusters there is a tendency towards an anitiferromagnetic arrangement of the magnetic moments of the two Cr atoms.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp01649d