Structure and stability of B+13 clusters

Gu, Feng; Yang, Xiaomei; Tang, An‐Na; Jiao, Haijun; Schleyer, Paul von Ragué

doi:10.1002/(sici)1096-987x(19980130)19:2<203::aid-jcc13>3.0.co;2-i

Cited by 89 publications

(95 citation statements)

References 28 publications

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“…[1][2][3][4][5][6][7][8][9][10][11][12] Experimentally boron clusters were produced and studied shortly after the discovery of the fullerenes primarily using mass spectrometry-based methods. [1][2][3][4][5][6][7][8][9][10][11][12] Experimentally boron clusters were produced and studied shortly after the discovery of the fullerenes primarily using mass spectrometry-based methods.…”

Section: Introductionmentioning

confidence: 99%

“…[19][20][21][22][23][24][25][26][27][28][29][30] Indeed, the combined experimental and theoretical investigations have shown that boron cluster anions are planar up to B 20 − , although for neutral clusters the global minimum of B 20 remains 3D. While earlier calculations suggested B 9 and B 9 + to be low symmetry 3D structures with C s symmetry, 5-7 the recent PES and theoretical study has shown that B 9 − and B 9 , in fact, possess unprecedented molecular wheel structures with an octacoordinate planar boron atom. 31 Among the small boron clusters, the nine-atom cluster is very special.…”

Section: Introductionmentioning

confidence: 99%

“…A recent ion mobility and theoretical study showed that for cations low-lying 3D structures appeared already at B 16 + . 22 The B 9 − anion has a perfect D 8h structure and is aromatic with six electrons, analogous to benzene, whereas the B 9 neutral cluster is predicted to possess a slightly distorted D 2h ͑ 2 B 1g ͒ structure due to the Jahn-Teller effect. While earlier calculations suggested B 9 and B 9 + to be low symmetry 3D structures with C s symmetry, 5-7 the recent PES and theoretical study has shown that B 9 − and B 9 , in fact, possess unprecedented molecular wheel structures with an octacoordinate planar boron atom.…”

Section: Introductionmentioning

confidence: 99%

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Low-lying isomers of the B9− boron cluster: The planar molecular wheel versus three-dimensional structures

Pan

Wang

2008

The Journal of Chemical Physics

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The B(9)(-) cluster was found previously to be an unprecedented molecular wheel containing an octacoordinate planar boron with D(8h) symmetry in a combined photoelectron spectroscopy (PES) and theoretical study [H. J. Zhai et al., Angew. Chem., Int. Ed. 42, 6004 (2003)]. However, the PES spectra of B(9)(-) exhibit minor features that cannot be explained by the global minimum D(8h) structure, suggesting possible contributions from low-lying isomers at finite temperatures. Here we present Car-Parrinello molecular dynamics with simulated annealing simulations to fully explore the potential energy surface of B(9)(-) and search for low-lying isomers that may account for the minor PES features. We performed density functional theory (DFT) calculations with different exchange-correlation functionals and ab initio calculations at various levels of theory with different basis sets. Two three-dimensional low-lying isomers were found, both of C(s) symmetry, 6.29 (C(s)-2) and 10.23 (C(s)-1) kcal/mol higher in energy than the D(8h) structure at the highest CCSD(T) level of theory. Calculated detachment transitions from the C(s)-2 isomer are in excellent agreement with the minor features observed in the PES spectra of B(9)(-). The B(9)(-) cluster proves to be a challenge for most DFT methods and the calculated relative energies strongly depend on the exchange-correlation functionals, providing an excellent example for evaluating the accuracies of various DFT methods.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Low-lying isomers of the B9− boron cluster: The planar molecular wheel versus three-dimensional structures

Pan

Wang

2008

The Journal of Chemical Physics

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“…[20][21][22] However, subsequent computational studies showed that icosahedral cage structures for B 12 and B 13 were unstable. [23][24][25][26][27][28][29][30] Chemical bonding analyses revealed that the concepts of aromaticity, multiple aromaticity/antiaromaticity, and conflicting aromaticity could nicely explain the geometries and stabilities of these quasi-planar boron clusters. [1][2][3][4][5][6][7][8][9][10][11][12][13][31][32][33][34] The following chemical bonding model was developed for planar boron clusters: all peripheral boron atoms are bonded to their neighbors by two-center two-electron (2c-2e) σ bonds, while the central atoms are bonded via delocalized multi-center σ and π bonds with the peripheral atoms.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy and ab initio study of boron-carbon mixed clusters: CB9− and C2B8−

Galeev

Romanescu

et al. 2012

The Journal of Chemical Physics

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We performed a joint photoelectron spectroscopy and ab initio study of two carbon-doped boron clusters, CB(9)(-) and C(2)B(8)(-). Unbiased computational searches revealed similar global minimum structures for both clusters. The comparison of the experimentally observed and theoretically calculated vertical detachment energies revealed that only the global minimum structure is responsible for the experimental spectra of CB(9)(-), whereas the two lowest-lying isomers of C(2)B(8)(-) contribute to the experimental spectra. The planar "distorted wheel" type structures with a single inner boron atom found for CB(9)(-) and C(2)B(8)(-) are different from the quasi-planar structure of B(10)(-), which consists of two inner atoms and eight peripheral boron atoms. The adaptive natural density partitioning chemical bonding analysis revealed that CB(9)(-) and C(2)B(8) clusters exhibit π aromaticity and σ antiaromaticity, which is consistent with their planar distorted structures.

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“…[50][51][52] Fowler and Ugalde 53 were the first who connected the stability and low reactivity of B þ 13 with the aromaticity generated by the delocalization of p-electrons of the filled molecular orbitals. They asserted that this special stability due to the aromatic character of the quasi-planar cluster similar to benzene.…”

Section: Icosahedral-based Crystalline Boronmentioning

confidence: 99%

Towards novel boron nanostructural materials

Boustani¹

Chemical Modelling

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Nanostructures are linked to many areas of science and technology. A cornerstone of our current research is the practical development of boron cluster-based, nanostructured Materials-by-Design. It is now possible to imagine and predictably model properties, synthesis procedures, manufacturing processes, and to functionally integrate engineering principles. Super-properties such as hardness, wear, coating, as a form of resistance to many attacks (e.g. corrosion), conductivity, spin and energy conversion/ storage, neutron protection and absorption, radiation shielding, armor, hardening, enforce, nanoenergetic, propulsion and glue materials, not to mention the boron neutron capture therapy in medicine, will benefit from the functionalization and industrialization of boron clusters and predicted nanostructures. The experimentally observed physical manifestations of a number of these clusters and nanostructures and related properties are consistent with our theoretical models. Early experiments have demonstrated the near-term viability of controlled synthesis for specific engineering properties.

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Structure and stability of B+13 clusters

Cited by 89 publications

References 28 publications

Low-lying isomers of the B9− boron cluster: The planar molecular wheel versus three-dimensional structures

Low-lying isomers of the B9− boron cluster: The planar molecular wheel versus three-dimensional structures

Photoelectron spectroscopy and ab initio study of boron-carbon mixed clusters: CB9− and C2B8−

Towards novel boron nanostructural materials

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