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Advances in the Theory of Atomic and Molecular Systems pp 201–215Cite as

Level-Structure and Magnetic Properties from One-Electron Atoms to Clusters with Delocalized Electronic Orbitals: Shell Models for Alkali Trimers

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Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 20))

Abstract

The triatomic alkali–metal clusters we investigate here are still accessible via molecular-orbital-based ab initio computation, but do already show some features characteristic of extended many-electron systems. Experimental observation of both the low-spin multiplicity (doublet) and the high-spin multiplicity (quartet) presents us with two species with very different binding mechanisms (covalent vs. van der Waals). The Complete Active Space Self Consistent Field method in combination with Multi Reference Rayleigh Schrödinger Perturbation Theory of second order is applied to the high-spin (quartet) states of all possible homonuclear and heteronuclear trimers of K and Rb. We calculate the first few electronically excited states and compare the results with the doublet system of K3 and Rb3. The classical shell model for metal trimers is briefly reviewed in relation to the low-spin configuration and compared with a new model we introduce to rationalize the significantly different level structure we observe for the high-spin. This structure turns out to be related to the eigenstates of the harmonic oscillator, a feature known from the description of single-particle states in quantum dots.

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Authors and Affiliations

  1. Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, A-8010, Graz, Austria

    Andreas W. Hauser, Carlo Callegari & Wolfgang E. Ernst

Authors
  1. Andreas W. Hauser
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  2. Carlo Callegari
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  3. Wolfgang E. Ernst
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Corresponding author

Correspondence to Andreas W. Hauser .

Editor information

Editors and Affiliations

  1. Department of Chemistry, Michigan State University, 48824, East Lansing, MI, USA

    Piotr Piecuch

  2. Laboratoire de Chimie Physique, CNRS and UPMC, 11 rue Pierre et Marie Curie, 75005, Paris, France

    Jean Maruani

  3. Instituto de Física Fundamental CSIC, Serrano, 123, E-28006, Madrid, Spain

    Gerardo Delgado-Barrio

  4. Physical & Theoretical Chemistry Laboratory, University of Oxford, South Parks Rd, OX1 3QZ, Oxford, United Kingdom

    Stephen Wilson

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Hauser, A.W., Callegari, C., Ernst, W.E. (2009). Level-Structure and Magnetic Properties from One-Electron Atoms to Clusters with Delocalized Electronic Orbitals: Shell Models for Alkali Trimers. In: Piecuch, P., Maruani, J., Delgado-Barrio, G., Wilson, S. (eds) Advances in the Theory of Atomic and Molecular Systems. Progress in Theoretical Chemistry and Physics, vol 20. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-2985-0_10

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