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Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB₂₄ (M = Sc, V, and Mn).

ABSTRACT: A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB₂₄ (M = Sc, V, and Mn) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the VB₂₄ and MnB₂₄ clusters correspond to cage structures. Interestingly, the global minima obtained for the ScB₂₄ cluster tend to a three-ring tubular structure. Population analyses and valence electron density analyses reveal that partial electrons on transition-metal atoms transfer to boron atoms. The localized orbital locator of MB₂₄ (M = Sc, V, and Mn) indicates that the electron delocalization of ScB₂₄ is stronger than that of VB₂₄ and MnB₂₄, and there is no obvious covalent bond between doped metals and B atoms. The spin density and spin population analyses reveal that MB₂₄ (M = Sc, V, and Mn) have different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The calculated spectra indicate that MB₂₄ (M = Sc, V, and Mn) has meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.

SUBMITTER: Yang YJ

PROVIDER: S-EPMC8600523 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the MB24 - (M = Sc, Ti, V, and Cr) clusters correspond to cage structures, and the MB24 - (M = Mn, Fe, and Co) clusters have similar distorted four-ring tubes with six boron atoms each. Interestingly, the global minima obtained for the NiB24 - cluster tend to a quasi-planar structure. Charge population analyses and valence electron density analyses reveal that almost one electron on the transition-metal atoms transfers to the boron atoms. The electron localization function (ELF) of MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) indicates that the local delocalization of MB24 - (M = Sc, Ti, V, Cr, and Ni) is weaker than that of MB24 - (M = Mn, Fe, and Co), and there is no obvious covalent bond between doped metal and B atoms. The spin density and spin population analyses reveal that open-shell MB24 - (M = Ti, Cr, Fe, and Ni) has different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The polarizability of MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) shows that MB24 - (M = Mn, Fe, and Co) has larger first hyperpolarizability, indicating that MB24 - (M = Mn, Fe, and Co) has a strong nonlinear optical response. Hence, MB24 - (M = Mn, Fe, and Co) might be considered as a promising nonlinear optical boron-based nanomaterial. The calculated spectra indicate that MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) has different and meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.

Project description:We present a theoretical study of structural evolution, electronic properties, and photoelectron spectra of two sulfur atom-doped boron clusters S2Bn0/- (n = 2-13), which reveal that the global minima of the S2Bn0/- (n = 2-13) clusters show an evolution from a linear-chain structure to a planar or quasi-planar structure. Some S-doped boron clusters have the skeleton of corresponding pure boron clusters; however, the addition of two sulfur atoms modified and improved some of the pure boron cluster structures. Boron is electron-deficient and boron clusters do not form linear chains. Here, two sulfur atom doping can adjust the pure boron clusters to a linear-chain structure (S2B20/-, S2B30/-, and S2B4-), a quasi-linear-chain structure (S2B6-), single- and double-chain structures (S2B6 and S2B9-), and double-chain structures (S2B5, and S2B9). In particular, the smallest linear-chain boron clusters S2B20/- are shown with an S atom attached to each end of B2. The S2B2 cluster possesses the largest highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap of 5.57 eV and the S2B2- cluster possesses the largest average binding energy Eb of 5.63 eV, which shows the superior chemical stability and relative stability, respectively. Interestingly, two S-atom doping can adjust the quasi-planar pure boron clusters (B7-, B10-, and B120/-) to a perfect planar structure. AdNDP bonding analyses reveal that linear S2B3 and planar SeB11- have π aromaticity and σ antiaromaticity; however, S2B2, planar S2B6, and planar S2B7- clusters have π antiaromaticity and σ aromaticity. Furthermore, AdNDP bonding analyses reveal that planar S2B4, S2B10, and S2B12 clusters are doubly (π and σ) aromatic, whereas S2B5-, S2B8, S2B9-, and S2B13- clusters are doubly (π and σ) antiaromatic. The electron localization function (ELF) analysis shows that S2Bn0/- (n = 2-13) clusters have different electron delocalization characteristics, and the spin density analysis shows that the open-shell clusters have different characteristics of electron spin distribution. The calculated photoelectron spectra indicate that S2Bn- (n = 2-13) have different characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these doped boron clusters. Our work enriches the new database of geometrical structures of doped boron clusters, provides new examples of aromaticity for doped boron clusters, and is promising to offer new ideas for nanomaterials and nanodevices.

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Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB₂₄ (M = Sc, V, and Mn).

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Dataset Information

Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB24 (M = Sc, V, and Mn).

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OmicsDI is part of the ELIXIR infrastructure

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Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB₂₄ (M = Sc, V, and Mn).