Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Lu, Sheng-Jie; Xu, Xi-Ling; Cao, Guo-Jin; Xu, Hong‐Guang; Zheng, Wei‐Jun

doi:10.1063/1.5052559

Cited by 19 publications

(12 citation statements)

References 72 publications

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“…The B n Si m clusters approach cage structures as the number of Si increases. 29,33,34,62 With m > n, the clusters would be equivalent of B n (BH) m clusters, i.e., with a greater number of boron atoms attached with H atoms. Here, with an increase in number of Si atoms, more electrons are removed from skeletal orbitals to Si lone pair orbitals.…”

Section: ■ Computational Detailsmentioning

confidence: 99%

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

2019

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The removal of H atoms from polyhedral boranes results in the formation of dangling radial orbitals with one electron each. If there is a requirement of electrons for skeletal bonding to meet the Wade's rule, these are provided from the exohedral orbitals. Additional electrons occupy a linear combination of the dangling orbitals. Stabilization of these molecular orbitals depends on their overlap. The lateral (sideways) overlap of dangling orbitals decreases with the decreasing cluster size from 12 to 5 boron atoms as the orbitals become more and more splayed out. Thus, as the number of dangling orbitals increases, the destabilization of their combinations increases at a higher rate for smaller polyhedral boranes, leading to flat structures with the removal of a fewer number of hydrogens. Though exohedral orbitals form better overlap in larger polyhedral clusters, the increase of electrons with the removal of H atoms results in occupancy of antibonding skeletal orbitals (beyond Wade's rules) and leads to flat structures. The reverse happens when hydrogens are added to a flat cluster. Substitution of BH by Si does not change structural patterns.

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Section: ■ Computational Detailsmentioning

confidence: 99%

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

2019

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“…Changes in composition of silicon materials, that is the incorporation of dopants such as boron or phosphorus, are typically achieved by admixture of diborane(6) (B 2 H 6 ) or phosphane (PH 3 ) at a late stage of silicon purification for band gap engineering in the crystalline state. − The superconductivity of cubic silicon at high boron concentrations and temperatures near 0 K constitutes an extreme manifestation of the effect of heteroatoms on electronic properties of silicon . While a few stable examples of heterosiliconoids containing heavier Group 14 elements, namely, germanium and tin, are known, − related species with Group 13 and/or 15 elements have so far only been observed in the gas phase or were calculated theoretically. − We recently reported the functionalization of the dismutational isomer ( 1 ) and the global minimum isomer ( 2 ) of the still hypothetical hexasilabenzene by reductive cleavage of one of the aryl substituents (Scheme ). As distinct functionalized derivatives of 2 were obtained regiospecifically in both cases, , the peculiar stability of this type of Si 6 scaffold became once more obvious.…”

Section: Introductionmentioning

confidence: 99%

Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters

et al. 2019

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Unsaturated silicon clusters (siliconoids) are short-lived intermediates during the transition from molecules to the elemental bulk; stable representatives reiterate surface features of silicon materials. The incorporation of suitable heteroatoms into the cluster scaffold of stable siliconoids extends this analogy to the technological process of silicon doping. Here, we report boron-and phosphorus-containing heterosiliconoids with BSi 5 and PSi 5 core based on the global minimum Si 6 R 6 platform (dubbed benzpolarene for its relationship to benzene). The reductive cleavage of an SiR 2 moiety (R = 2,4,6-iPr 3 C 6 H 2 ) from Si 6 R 6 selectively yields a dianionic Si 5 R 4 2− cluster as its lithium salt. Treatment with Me 3 SiCl affords the corresponding trimethylsilyl-substituted (Me 3 Si) 2 Si 5 R 4 . Reaction of Si 5 R 4 2− with iPr 2 NECl 2 (E = B, P) yields the unprecedented p-and n-doped heterosiliconoids iPr 2 NESi 5 R 4 . Their peculiar electronic features are compared to those of the hexasilabenzpolarene starting material on grounds of NMR spectroscopy, X-ray diffraction, and DFT calculations.

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“…Our first and foremost note is that the most stable anionic I.B 2 Si 3 − structure (Figure 1) located in the present study was not found in the previous report by Lu and co-workers. 41 The anionic isomer II.B 2 Si 3 − , which was assigned as the global minimum of B 2 Si 3 − by these authors, 41 is now found at 2.7 kcal/mol higher in energy than the new I.B 2 Si 3 − , even though it remains competitive for the ground state in view of such a small energy difference. Such an omission by Lu et al 41 could have been due to the fact that they used the B3LYP functional in their search for stable structures.…”

Section: ■ Computational Methodsmentioning

confidence: 94%

“…41 The anionic isomer II.B 2 Si 3 − , which was assigned as the global minimum of B 2 Si 3 − by these authors, 41 is now found at 2.7 kcal/mol higher in energy than the new I.B 2 Si 3 − , even though it remains competitive for the ground state in view of such a small energy difference. Such an omission by Lu et al 41 could have been due to the fact that they used the B3LYP functional in their search for stable structures. Indeed, Koukaras 42 subsequently showed the erroneous performance of this hybrid functional on geometries of mixed boron clusters.…”

Section: ■ Computational Methodsmentioning

confidence: 94%

“…The B 2 Si 3 −/0 species were previously investigated by Lu et al 41 using anion photoelectron spectroscopy and calculations. On the basis of the calculated CCSD results, Koukaras 42 subsequently concluded that the neutral B 2 Si 3 is stable in a planar form, in contrast to previous results by calculations and experimental infrared spectroscopy reported by Truong and co-workers 43 that showed that it is slightly distorted from planarity.…”

Section: ■ Computational Methodsmentioning

confidence: 99%

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Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons

et al. 2022

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The small binary boron silicon clusters B2Si3 q with q going from −2 to +2 and B3Si2 p with p varying from −3 to +1 were reinvestigated using quantum chemical methods. The thermodynamic stability of these smallest ribbon structures is governed by both Hückel and ribbon models for aromaticity. The more negative the cluster charge, the more ribbon character is shown. In contrast, the more positive the charge state, the more pronounced the Hückel character becomes. The ribbon aromaticity character can also be classified into ribbon aromatic, semiaromatic, antiaromatic, and triplet aromatic when the electron configuration of a ribbon structure is described as [...π 2(n+1) σ 2n ], [...π 2n+1 σ 2n ], [...π 2n σ 2n ], and [...π 2n+1 σ 2n–1 ], respectively. Geometry optimizations of the B2Si3 lowest-energy structure by some density functional theory (DFT) functionals result in a nonplanar shape because it possesses an antiaromatic ribbon character. However, its π aromaticity assigned by the Hückel rule is stronger in such a way that several other DFT and coupled-cluster theory CCSD(T) calculations show that B2Si3 is indeed stable in a planar form (C s ). A new global equilibrium structure for the anion B2Si3 2–, which is a ribbon semiaromatic species, was identified. Some benchmark tests were also carried out to evaluate the performance of popular methods for the treatment of binary B–Si clusters. At odds with some previous studies, we found that with reference to the high accuracy CCSD(T)/CBS method, the hybrid TPSSh functional is reliable for a structure search, whereas the hybrid B3LYP functional is more suitable for simulations of some experimental spectroscopic results.

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Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Cited by 19 publications

References 72 publications

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters

Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons

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Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Cited by 19 publications

References 72 publications

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral BnHn–x Isomers (n = 5–12, x = 0 to n – 1)

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral BnHn–x Isomers (n = 5–12, x = 0 to n – 1)

Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters

Boron Silicon B2Si3qand B3Si2pClusters: The Smallest Aromatic Ribbons

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Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

Overlap of Radial Dangling Orbitals Controls the Relative Stabilities of Polyhedral B_nH_n–x Isomers (n = 5–12, x = 0 to n – 1)

Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons