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Electronic structure studies of diradicals derived from Closo-Carboranes

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Abstract

Electronic structure computations have been performed on diradical systems composed of two carborane radicals CB11H12 · connected through acetylene, ethylene and ethane bridge units, leading, respectively, to a linear and two trans structures. Each cage possesses one unpaired electron and the total system can thus be coupled to a singlet or a triplet state. Numerical determinations using the spin-projected method with a hybrid B3LYP functional show that these compounds have singlet ground states with low singlet–triplet energy gaps of 0.004 eV (acetylene bridge), 0.080 eV (ethylene bridge) and 0.0005 eV (ethane bridge). Spin population analyses point out a left/right localized spin distribution in the spin-projected wave function. The possibility of mapping these results onto a Heisenberg spin Hamiltonian is considered, in order to predict low-lying excited states in extended carborane chains.

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Acknowledgments

This report has been financially supported by the Projects MICINN CTQ2009-13652, UBACYT 20020100100197 (Universidad de Buenos Aires), PIP No. 11220090100061 (Consejo Nacional de Investigaciones Científicas y Técnicas, República Argentina), GIU09/43 (Universidad del País Vasco) and UFI11/07 (Universidad del País Vasco). We thank the Universidad del País Vasco for allocation of computational resources.

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Authors and Affiliations

  1. Instituto de Química-Física “Rocasolano”, Consejo Superior de Investigaciones Científicas, 28006, Madrid, Spain

    Josep M. Oliva

  2. Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, 1428, Buenos Aires, Argentina

    Diego R. Alcoba

  3. Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428, Buenos Aires, Argentina

    Diego R. Alcoba

  4. Departamento de Química Física. Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, 48080, Bilbao, Spain

    Luis Lain & Alicia Torre

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  1. Josep M. Oliva
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  2. Diego R. Alcoba
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  3. Luis Lain
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  4. Alicia Torre
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Correspondence to Josep M. Oliva.

Additional information

Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).

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Oliva, J.M., Alcoba, D.R., Lain, L. et al. Electronic structure studies of diradicals derived from Closo-Carboranes. Theor Chem Acc 132, 1329 (2013). https://doi.org/10.1007/s00214-012-1329-1

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