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Quantum Mechanical Modeling of Structure Evolution of Transition Metal Clusters and Metallocarbohedrenes

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Book cover Implications of Molecular and Materials Structure for New Technologies

Part of the book series: NATO Science Series ((NSSE,volume 360))

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Abstract

Ab initio quantum-mechanical modeling based on density functional theory (DFT) was used to study transition metal clusters and metallo-carbohedrenes (MetCars). Combined with the state-of-the-art spectroscopic experiments, DFT calculations are capable of yielding much insight into the structures, chemical bonding and growth mechanisms of these clusters. Two specific cluster systems were investigated in detail: one involves small chromium clusters and another contains titanium carbides. Exhaustive structural search was performed by fully optimizing a variety of cluster geometries. For the chromium clusters, we found that a tightly-bound Cr2 dimer plays a key role in determining the cluster structures. A dimer growth route is discovered for clusters up to Cr11, at which a structural transition occurs from the dimer growth to a bulk-like body-centered-cubic structure. The uncovered structural evolution is consistent with the currently available experimental observations. For MetCars, we found that three factors, i.e., the C2 dimer, cubic framework and layered structures, play an essential role in determining the structures and chemical bonding of the titanium carbide clusters. A growth pathway from Ti3C8 to Ti13C22 with Ti4C8, Ti6C13, Ti7C13 and Ti9C15 as intermediates is thus proposed. Both theory and experiments suggest that the cubic layered growth with C2 dimers can lead to a new type of highly stable one-dimensional quantum wires.

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Author information

Authors and Affiliations

  1. Air Products and Chemicals, Inc., 7201 Hamilton Boulevard, Allentown, PA, 18195-1501, USA

    Hansong Cheng

  2. Department of Physics, Washington State University, Richland, WA, 99352, USA

    Lai-Sheng Wang

  3. W. R. Wiley Environmental Molecular Sciences Laboratory, MS K8-88, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Lai-Sheng Wang

Authors
  1. Hansong Cheng
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  2. Lai-Sheng Wang
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Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, UK

    Judith A. K. Howard

  2. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK

    Frank H. Allen  & Gregory P. Shields  & 

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© 1999 Springer Science+Business Media Dordrecht

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Cheng, H., Wang, LS. (1999). Quantum Mechanical Modeling of Structure Evolution of Transition Metal Clusters and Metallocarbohedrenes. In: Howard, J.A.K., Allen, F.H., Shields, G.P. (eds) Implications of Molecular and Materials Structure for New Technologies. NATO Science Series, vol 360. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4653-1_10

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  • DOI: https://doi.org/10.1007/978-94-011-4653-1_10

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-5817-6

  • Online ISBN: 978-94-011-4653-1

  • eBook Packages: Springer Book Archive

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