Novel architectures of boron

Gribanova, T. N.; Minyaev, R. M.; Минкин, В. И.; Boldyrev, Alexander I.

doi:10.1007/s11224-020-01606-9

Cited by 19 publications

(10 citation statements)

References 129 publications

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“…Beryllium-doped boron clusters exhibit remarkable properties such as fluxionality [ 7 , 21 , 31 , 53 , 54 , 55 ] and aromaticity [ 21 , 56 ], as well as characteristics similar to borophene [ 57 ]. Previous theoretical studies have shown that the boron fullerenes B 60 and B 80 can be stabilized by surrounding the boron clusters with beryllium atoms [ 58 , 59 ], which effectively compensates for boron electronic deficiency [ 59 ]. These effects make beryllium-doped boron clusters interesting research objects.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

et al. 2021

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Lowest-energy structures, the distribution of isomers, and their molecular properties depend significantly on geometry and temperature. Total energy computations using DFT methodology are typically carried out at a temperature of zero K; thereby, entropic contributions to the total energy are neglected, even though functional materials work at finite temperatures. In the present study, the probability of the occurrence of one particular Be4B8 isomer at temperature T is estimated by employing Gibbs free energy computed within the framework of quantum statistical mechanics and nanothermodynamics. To identify a list of all possible low-energy chiral and achiral structures, an exhaustive and efficient exploration of the potential/free energy surfaces is carried out using a multi-level multistep global genetic algorithm search coupled with DFT. In addition, we discuss the energetic ordering of structures computed at the DFT level against single-point energy calculations at the CCSD(T) level of theory. The total VCD/IR spectra as a function of temperature are computed using each isomer’s probability of occurrence in a Boltzmann-weighted superposition of each isomer’s spectrum. Additionally, we present chemical bonding analysis using the adaptive natural density partitioning method in the chiral putative global minimum. The transition state structures and the enantiomer–enantiomer and enantiomer–achiral activation energies as a function of temperature evidence that a change from an endergonic to an exergonic type of reaction occurs at a temperature of 739 K.

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Section: Introductionmentioning

confidence: 99%

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

et al. 2021

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“…In contrast, doping a boron cluster with metals [7,9,24,[41][42][43] like beryllium-doped boron clusters, exhibit remarkable properties such as fluxionality [16,29,32,[44][45][46], aromaticity [29,47], and characteristics similar to borophene [1]. Furthermore, previous theoretical studies showed that the boron fullerenes B 60 and B 80 can be stabilized by surrounding the boron clusters with beryllium atoms [48,49], which effectively compensates for boron electronic deficiency [49]. These effects make beryllium-doped boron clusters interesting, joined with the fact, nowadays, dynamic structural fluxionality in boron nanoclusters is a topic of interest in nanotechnology [19,50].…”

Section: Introductionmentioning

confidence: 99%

Boltzmann Populations of the Fluxional Be₆B₁₁⁻ and Chiral Be₄B₈ Clusters at Finite Temperatures Computed by DFT and Statistical Thermodynamics

Buelna-Garcia¹,

Castillo-Quevedo²,

Paredes-Sotelo³

et al. 2022

Density Functional Theory - Recent Advances, New Perspectives and Applications

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Total energy computations using density functional theory are typically carried out at a zero temperature; thus, entropic and thermic contributions to the total energy are neglected, even though functional materials work at finite temperatures. This book chapter investigates the Boltzmann populations of the fluxional Be6B11− and chiral Be4B8 isomers at finite temperature estimated within the framework of density functional theory, CCSD(T), and statistical thermodynamics. A couple of steps are taken into account to compute the Boltzmann populations. First, to identify a list of all possible low-energy chiral and achiral structures, an exhaustive and efficient exploration of the potential/free energy surfaces is carried out using a multi-level and multi-step global hybrid genetic algorithm search coupled with Gaussian code. Second, the thermal or so-called Boltzmann populations were computed in the framework of statistical thermodynamics for temperatures ranging from 20 to 1500 K at DFT and CCSD(T) theoretical levels. The results show the effects of temperature on the distribution of isomers define the putative global minimum at finite temperature due to the minimization of the Gibbs free energy and maximization of entropy. Additionally, we found that the fluxional Be6B11− cluster is strongly dominant at hot temperatures, whereas the chiral Be4B8 cluster is dominant at room temperature. The methodology and results show the thermal effects in the relative population hence molecular properties.

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“…), overall their experimental realization remains a challenge. 2D boron, − borophene, is perhaps a rare example where theory has also guided , the first successful synthesis. , In contrast, material with structural units in planar or linear coordination could practically retain its chemical bonding in lower dimensions, without a significant increase of energy, and therefore is a more likely candidate to be synthesized in low-D form as compared to the above examples.…”

Section: Introductionmentioning

confidence: 99%

Stable Low-Dimensional Boron Chalcogenides from Planar Structural Motifs

et al. 2021

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There has been growing interest in searching for new low-dimensional (low-D) materials for nanoelectronics and energy applications. Most materials have their structural units extended in three dimensions and connected with chemical bonds. When the dimension is reduced, these bonds will be broken, decreasing the stability and making their experimental realization difficult. Here, we show that stable low-D materials can be made from naturally existing planar structural units. This is demonstrated by first-principles study of boron chalcogenides (B–X), which can have various low-D structures with attractive properties. For example, B2O3 can be the thinnest proton-exchange membrane for fuel cells. B–X are wide-gap semiconductors that can complement the narrow-gap 2D metal dichalcogenides for (opto)electronics. Our work sheds light on the stability of low-D materials and suggests guidelines for rational design of new materials.

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Novel architectures of boron

Cited by 19 publications

References 129 publications

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Boltzmann Populations of the Fluxional Be₆B₁₁⁻ and Chiral Be₄B₈ Clusters at Finite Temperatures Computed by DFT and Statistical Thermodynamics

Stable Low-Dimensional Boron Chalcogenides from Planar Structural Motifs

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Novel architectures of boron

Cited by 19 publications

References 129 publications

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Boltzmann Populations of the Fluxional Be6B11− and Chiral Be4B8 Clusters at Finite Temperatures Computed by DFT and Statistical Thermodynamics

Stable Low-Dimensional Boron Chalcogenides from Planar Structural Motifs

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Product

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Boltzmann Populations of the Fluxional Be₆B₁₁⁻ and Chiral Be₄B₈ Clusters at Finite Temperatures Computed by DFT and Statistical Thermodynamics