Small Carbon Clusters:  Spectroscopy, Structure, and Energetics

Orden, Alan Van; Saykally, Richard J.

doi:10.1021/cr970086n

Cited by 594 publications

(584 citation statements)

References 307 publications

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“…Instead, a more likely reason is the directional bonding found in both systems. For the few elemental systems of this type (e.g., C [23], B [3], Si [1,2], Ge [24]) it has been established by experimental and theoretical means that structural transitions occur for nanoscale clusters. Most other elements form relatively densely packed clusters via isotropic interatomic interactions (e.g., metallic, dispersive) and do not display such rich structural behavior.…”

Section: -2mentioning

confidence: 99%

Columnar-to-Disk Structural Transition in Nanoscale(SiO2)NClusters

Bromley

Flikkema

2005

Phys. Rev. Lett.

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Extensive large-scale global optimizations refined by ab initio calculations are used to propose SiO 2 N N 14-27 ground states. For N < 23 clusters are columnar and show N-odd-N-even stability, energetically and electronically. At N 23 a columnar-to-disk structural transition occurs reminiscent of that observed for Si N . These transitions differ in nature but have the same basis, linking the nanostructural behavior of an element (Si) and its oxide (SiO 2 ). Considering the impact of devices based on the nanoscale manipulation of Si=SiO 2 the result is of potential technological importance. DOI: 10.1103/PhysRevLett.95.185505 PACS numbers: 61.46.+w, 36.40.Ei, 36.40.Mr, 68.65.2k The technological importance of nanoscale silica (SiO 2 ) can hardly be overstated considering its established utilization in microelectronics, catalysis, and composite materials and its promise in the emerging field of photonics. Although much experimental and theoretical work has focused upon the stabilities and structures of the many silica bulk polymorphs and their surfaces, the low energy structures and potential energy surface (PES) of nanoscale SiO 2 clusters is relatively unknown. In this Letter we provide the beginnings of an energetic baseline of the complex PES of nanoscale SiO 2 by finding the lowest energy forms of silica for SiO 2 N N 14-27 providing new limits on the stability of this centrally important material in the physical, chemical, and geophysical sciences. The clusters we study all have at least one dimension between 1 and 2.5 nm and are all substantially lower in energy than any previously reported. Our results strongly indicate that one-dimensional columnar structures are energetically favored up to a length scale of at least 2 nm where upon a transition to two-dimensional trigonal disklike structures occurs at N 23. The transition is characterized by sharp changes in measures of the structural form, electronic structure, and bonding topology of the cluster series, but appears smooth with respect to cluster energies. The structural transition in SiO 2 N clusters is compared to that known for clusters of its parent element Si N [1]. In both cases for N 23-25 a structural transition from elongated to more compact forms appears to occur in the thermodynamically preferred clusters [2]. Usually oxides and their parent elements display different but complementary physical and chemical properties and typically bear little structural relation to one another. Our finding that, at the nanoscale, the size-dependent structural behavior of SiO 2 and its parent element follow a similar general pattern is at once relatively unexpected and fundamentally suggests an inherent link between the two materials. Because of the immense dependence on the combined structural and physical properties of both nanoscale Si and SiO 2 in electronic and optical devices, our demonstration of such a connection is of potential significant technological importance.Although relatively small, M 20 homogeneous clusters of low atomic weight atoms are...

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Section: -2mentioning

confidence: 99%

Columnar-to-Disk Structural Transition in Nanoscale(SiO2)NClusters

Bromley

Flikkema

2005

Phys. Rev. Lett.

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“…The aim of this paper is to provide these values for small C q+ n carbon clusters (n = 2 − 12 and q = 0 − 2). A large number of theoretical studies focussing on the structural properties of these systems can be found in the literature (see the reviews [20,21] and references therein), but there is no theoretical work that treats all the clusters at the same level of theory. In order to obtain the energetic properties presented in this work, we have consistently evaluated neutral, singly-and doubly-charged small carbon clusters at the same level of theory.…”

Section: Introductionmentioning

confidence: 99%

Ionization potentials, dissociation energies and statistical fragmentation of neutral and positively charged small carbon clusters

Díaz‐Tendero¹,

Sánchez‐Sanz²,

Hervieux³

et al. 2006

Braz. J. Phys.

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Dissociation energies, ionization potentials and fragmentation dynamics of neutral, singly-and doubly charged small carbon clusters have been theoretically studied with a combination of the density functional theory, the coupled cluster method and the the statistical model microcanonical Metropolis Monte Carlo. The second ionization potential decreases with the cluster size and is larger than the first one, which also decreases with the size showing oscillations. Dissociation energies also oscillate with the cluster size, being those with an odd number of atoms more stable. C 3 cluster has the largest dissociation energy. The combination of a statistical treatment for the cluster fragmentation with experimental results has allowed us to evaluate the energy distribution in collisions experiments.

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“…Microwave, 1 infrared, 2 and UV-VIS spectra 3,4 are available both from matrix and gas-phase studies, all of them having in common that the major part of the observed geometries is linear. Even for very long chains, such as HC 22 H ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

High-resolution electronic spectroscopy of a nonlinear carbon chain radical C6H4+

Araki

Linnartz

Cias

et al. 2003

The Journal of Chemical Physics

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A high-resolution gas-phase spectrum of a molecular absorption band around 604 nm is assigned as due to an electronic transition of a nonlinear C 6 H 4 ϩ planar species starting from its 2 AЉ electronic ground state. The spectrum is observed in direct absorption by cavity ringdown spectroscopy through a supersonic planar discharge through a mixture of acetylene in helium. The spectrum has a clear rotational and K-type structure. This allows an accurate determination of the B and C rotational constants and an estimate for the A rotational constant in ground and electronically excited states. The resolved spectrum of the fully deuterated species C 6 D 4 ϩ has been obtained as well. The results are compared both to the outcome of ab initio geometry optimizations and low-resolution absorption spectra in 6 K neon matrices obtained after mass-selective deposition.

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Small Carbon Clusters: Spectroscopy, Structure, and Energetics

Cited by 594 publications

References 307 publications

Columnar-to-Disk Structural Transition in Nanoscale(SiO2)NClusters

Columnar-to-Disk Structural Transition in Nanoscale(SiO2)NClusters

Ionization potentials, dissociation energies and statistical fragmentation of neutral and positively charged small carbon clusters

High-resolution electronic spectroscopy of a nonlinear carbon chain radical C6H4+

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