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Orbital Localization-Driven Disruption of Peripheral Bonding in Valence-Isoelectronic B12 - Clusters
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DOI：10.1021/acs.jpca.6c00814.png)
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Abstract
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We present a systematic theoretical study of a valence-isoelectronic substitution series based on the quasi-planar B12 - cluster, elucidating the effects of heavier Group 13 dopants (Al, Ga, and In) on its geometric and electronic structure. Unbiased global minimum (GM) searches using the Coalescence Kick (CK) algorithm across doublet and quartet spin states identify the most stable structures of B12 -, AlB11 -, GaB11 -, InB11 -, Al2B10 -, Ga2B10 -, AlGaB10 -, GaInB10 -, and Al3B9 - clusters. Relative energetics of GMs and low-lying isomers are obtained at the DLPNO-CCSD(T)/aug-cc-pVTZ//U-TPSSh-D4/def2-TZVPD level. Our results show that the B12 --like motif persists up to two substitutions (Al2B10 -, Ga2B10 -) and in the mixed-metal composition (AlGaB10 -), where dopants occupy peripheral sites and preserve strong localized two-centertwo-electron (2c-2e) sigma bonding. Adaptive Natural Density Partitioning (AdNDP) analysis reveals that localization of a single unpaired electron (1c-1e) in an s-type orbital on the dopant atom replaces the fully delocalized pi-bonding orbital of the parent cluster. This localization induces substantial geometric puckering while retaining the peripheral 2c-2e sigma framework and, qualitatively, the B12 --like core. In contrast, when orbital localization progresses to formation of an s-type lone pair (1c-2e) on one Al atom in Al3B9 -, the valence-isoelectronic principle breaks down, leading to rupture of the peripheral bonding network and a transition to a three-dimensional structure. Similarly, incorporation of a single In atom causes pronounced deviation from the parent B12 - geometry in both InB11 - and GaInB10 -, driven by analogous 1c-2e lone-pair formation on the substituted atom arising from the enhanced s-orbital stabilization and increased s-p splitting.
Keywords:
CORRELATED MOLECULAR CALCULATIONS
GAUSSIAN-BASIS SETS
DOUBLE-HEXAGONAL VACANCY
MAIN-GROUP ELEMENTS
BORON CLUSTERS
PHOTOELECTRON-SPECTROSCOPY
AB-INITIO
ELECTRONIC-STRUCTURE
ALUMINUM CLUSTERS
QUASI-PLANAR
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