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Magnetic Properties of Conjugated Hydrocarbons from Topological Hamiltonians

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Applications of Topological Methods in Molecular Chemistry

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 22))

Abstract

The present chapter shows first that the topological Hückel Hamiltonian provides an analytical expression of both the singly occupied Molecular Orbitals and the spin density distribution of mono- and poly-radical conjugated hydrocarbons. It permits a new derivation of the Ovchinnikov’s rule (first established from a magnetic model Hamiltonian), which predicts the preferred ground state spin multiplicity from the topology of the molecule. From the Hubbard simplified representation of the bi-electronic Hamiltonian one obtains directly, without any matrix diagonalization, a reasonable evaluation of the singlet-triplet energy difference. For singlet di-radicals the method enables one to predict whether the Ms = 0 single-determinant solution is subject to a spin-symmetry breaking. The spin polarization of the closed shells, which is a different phenomenon, of bi-electronic origin, increases the value of the magnetic coupling in these systems, contrasts the spin densities between negative and positive values and spatially extends the spin distribution. Numerical Unrestricted Density Functional Theory calculations illustrate the relevance of the predictions of the topological model.

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Authors and Affiliations

  1. Laboratoire de Chimie et Physique Quantiques, UMR 5626 (CNRS), IRSAMC, Université P. Sabatier, 118 Rte de Narbonne, 31062, Toulouse Cedex, France

    Jean-Paul Malrieu & Nathalie Guihéry

  2. Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, 13397, Marseille Cedex 20, France

    Nicolas Ferré

Authors
  1. Jean-Paul Malrieu
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  2. Nicolas Ferré
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  3. Nathalie Guihéry
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Corresponding author

Correspondence to Jean-Paul Malrieu .

Editor information

Editors and Affiliations

  1. LCC-CNRS, Toulouse, France

    Remi Chauvin

  2. LCC-CNRS, Toulouse, France

    Christine Lepetit

  3. Théorique, UMR 761, Laboratoire de Chimie, Paris, France

    Bernard Silvi

  4. CNRS/UPM, MONARIS UMR 8233 (LADIR + LM2N), Paris, France

    Esmail Alikhani

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Malrieu, JP., Ferré, N., Guihéry, N. (2016). Magnetic Properties of Conjugated Hydrocarbons from Topological Hamiltonians. In: Chauvin, R., Lepetit, C., Silvi, B., Alikhani, E. (eds) Applications of Topological Methods in Molecular Chemistry. Challenges and Advances in Computational Chemistry and Physics, vol 22. Springer, Cham. https://doi.org/10.1007/978-3-319-29022-5_14

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