The Stone–Wales transformation: from fullerenes to graphite, from radiation damage to heat capacity

Heggie, M. I.; Haffenden, G.; Latham, Chris; Trevethan, Thomas

doi:10.1098/rsta.2015.0317

Cited by 13 publications

(8 citation statements)

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“…The dimerization of a [60]fullerene (C 60 ) van der Waals (vdW) dimer forming a short carbon nanotube (CNT) is probably the most frequently studied transformation in the field of carbon chemistry and has been observed under high pressure, high temperature, , metal reduction, light and electron irradiation, − as well as mechanochemical conditions. − Osawa and Tomanek proposed by theory the shortest possible path of this transformation from the vdW dimer OT-0 (Figure a), which is initiated by a cycloaddition/retrocycloaddition (Figure b), followed by a series of Stone–Wales rearrangements , (Figure c) to a D 5 d symmetry (5,5) CNT OT-24 . , Although the structure of the first long-lived intermediate, the [2 + 2] cycloadduct ( OT-1 ), was identified using X-ray diffraction and by high-resolution transmission electron microscopy (TEM), no other structures have been experimentally verified because of either their short lifetimes or the structural inhomogeneity and complexity of the intermediates. Typical for such fast cascade reactions are the many temporally overlapping transient intermediates, which appear and disappear stochastically during the transformation (Figure d).…”

Section: Introductionmentioning

confidence: 99%

Time-Resolved Imaging of Stochastic Cascade Reactions over a Submillisecond to Second Time Range at the Angstrom Level

et al. 2022

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Many chemical reactions, such as multistep catalytic cycles, are cascade reactions in which a series of transient intermediates appear and disappear stochastically over an extended period. The mechanisms of such reactions are challenging to study, even in ultrafast pump–probe experiments. The dimerization of a van der Waals dimer of [60]fullerene producing a short carbon nanotube is a typical cascade reaction and is probably the most frequently studied in carbon materials chemistry. As many as 23 intermediates were predicted by theory, but only the first stable one has been verified experimentally. With the aid of fast electron microscopy, we obtained cinematographic recordings of individual molecules at a maximum frame rate of 1600 frames per second. Using Chambolle total variation algorithm processing and automated cross-correlation image matching analysis, we report on the identification of several metastable intermediates by their shape and size. Although the reaction events occurred stochastically, varying the lifetime of each intermediate accordingly, the average lifetime for each intermediate structure could be obtained from statistical analysis of many cinematographic images for the cascade reaction. Among the shortest-living intermediates, we detected one that lasted less than 3 ms in three independent cascade reactions. We anticipate that the rapid technological development of microscopy and image processing will soon initiate an era of cinematographic studies of chemical reactions and cinematic chemistry.

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Section: Introductionmentioning

confidence: 99%

Time-Resolved Imaging of Stochastic Cascade Reactions over a Submillisecond to Second Time Range at the Angstrom Level

et al. 2022

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“…The SW defects have been widely found in graphene, [41] carbon nanotubes, [42] and fullerenes. [43] Meanwhile, both SV and double vacancies are widely reported in experiments through a high-resolution transmission electron microscope (HRTEM). [44] The ISW is one forecasting defects by density functional theory calculations.…”

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confidence: 99%

“…[46] Besides, the SW rearrangement has important implications for the chemical, electrical, and mechanical properties of carbon materials. [43] On the contrary, the QV defect presents the largest formation energy of 0.40 eV prim −1 , which is attributed to the relatively unstable C4 structure in the carbon plane. The formation energies of the other defects are about 0.20 eV prim −1 .…”

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confidence: 99%

The Defect Chemistry of Carbon Frameworks for Regulating the Lithium Nucleation and Growth Behaviors in Lithium Metal Anodes

Chen

Bai

et al. 2021

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cycles, finally resulting in capacity fading, but also can penetrate through the separator, causing the short circuit and safety hazards. [8,14,15] Constructing a composite Li metal anode framework has been strongly considered to both retard the formation of Li dendrites and reduce the volume expansion. [14,[16][17][18][19][20] Among various host candidates, carbon materials, including carbon nanotubes, [21] graphene, [22,23] graphite paper, [24] graphene balls, [25] and carbon nanospheres, [26,27] have been widely probed due to their lightweight, high electrical conductivity, and large specific surface area. Pure carbon can only afford a weak interaction with Li metal, which renders a high specific interfacial energy and a large nucleation barrier. Therefore, heteroatomdoping strategies are often adopted to enhance the electrochemical performance of carbon hosts, and the working mechanism of doping sites is comprehensively investigated. [3,22,28] For instance, Foroozan et al. constructed a 3D conformal graphene oxide nanosheet to effectively regulate uniform Li deposition. [29] Through scanning electron microscopy and optical observations, they demonstrated that a dense and uniform deposition of Li could be achieved by the 3D conformal graphene oxide nanosheet.Defects are almost inevitably introduced during the synthesis of various carbon materials, especially the heteroatomdoped carbon. [3,[30][31][32] More importantly, carbon atoms in defects often play as the active sites in surface reactions as the unsaturated-coordination nature affords them a stronger interaction with reactants than the other atoms. In Li metal batteries, defective graphene was reported to increase the Coulombic efficiency and prevent dendritic growth. [33,34] However, Liu et al. reported that pristine graphene (PG) yields state-ofthe-art electrochemical performance with the post cycled metal surface, which is relatively smoother and more dendrite-free than defective graphene. [35] The different results induced by defects are originated from various defect types. Therefore, it is very important to understand the fundamental role of various defects in regulating the Li nucleation. If a comprehensive and deep understanding of defect chemistry can be built, highly lithiophilic carbon materials can be rationally designed through both defect engineering and heteroatom-doping strategies.

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“…For a cluster consisting of 60 carbon atoms, the most appealing impression may be the discovery of buckminsterfullerene (BF) with a football-cage structure [30]. Following investigations revealed that, besides the lowest potential-energy BF, there exists a bunch of C 60 isomers, such as those introduced by the Stone-Wales (SW) rearrangement [31]. For a long time, researches [32][33][34] have been attempting to answer the very questions whether the isomers are able to survive in realistic systems at finite temperatures and what the probability relative to BF is.…”

Section: A For Isomers Of C60 Moleculementioning

confidence: 99%

Solution to the key problem of statistical physics -- calculations of partition function of many-body systems

Ning,

Gong,

Weng

et al. 2019

Preprint

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The key problem of statistical physics standing over one hundred years is how to exactly calculate the partition function (or free energy) of many-body interaction systems, which severely hinders application of the theory for realistic systems. Here we present a novel approach that works at least four orders faster than state-of-the-art algorithms to the problem and can be applied to predict thermal properties of large molecules or macroscopic condensed matters via ab initio calculations. The method was demonstrated by C60 molecules, solid and liquid copper (up to ∼ 600GPa), solid argon, graphene and silicene on substrate, and the derived internal energy or pressure is in a good agreement with the results of vast molecular dynamics simulations in a temperature range up to 2500K, achieving a precision at least one order higher than previous methods. And, for the first time, the realistic isochoric equation of state for solid argon was reproduced directly from the partition function. II. DIRECT INTEGRAL APPROACH TO PARTITION FUNCTIONThe original sense of one-fold (1D) integral I 1D = a1 0 f (x)dx is interpreted as the sum of infinite number of rectangles with area A i = f (x i )∆x, and I 1D =

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The Stone–Wales transformation: from fullerenes to graphite, from radiation damage to heat capacity

Abstract: One contribution of 12 to a theme issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene' .

Cited by 13 publications

References 61 publications

Time-Resolved Imaging of Stochastic Cascade Reactions over a Submillisecond to Second Time Range at the Angstrom Level

Time-Resolved Imaging of Stochastic Cascade Reactions over a Submillisecond to Second Time Range at the Angstrom Level

The Defect Chemistry of Carbon Frameworks for Regulating the Lithium Nucleation and Growth Behaviors in Lithium Metal Anodes

Solution to the key problem of statistical physics -- calculations of partition function of many-body systems

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