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Understanding the impact of correlation on bond length alternation in polyenes

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Abstract

This article analyzes the electronic factors governing bond length alternation (BLA) in linear polyenes. The impact of the various effects is illustrated on small all-trans polyenes, namely butadiene, hexatriene and octatetraene prototype molecules. It is well known that self-consistent-field single determinant treatments overestimate the bond length alternation and the paper aims to identify physical effects of correlation which correct this defect. The question is addressed using an orthogonal valence bond-type formalism in which the wave function is expressed in terms of strongly localized bonding and antibonding molecular orbitals. This paper shows that dynamic polarization effects of π orbitals accounted for in the full-π complete active space wave function significantly reduce bond alternation. These effects are brought by single excitations applied on the inter-bond charge transfer determinants. The dynamic polarization of σ bonds, of either CC or CH character, is analyzed afterward by either enlarging the active space or by adding the 1hole-1particle excitations. It is shown that these effects also decrease the BLA and increase the coefficients of the charge transfer determinants. Moreover, the relation with dynamic polarization of ligand-to-metal and metal-to-ligand charge transfer (LMCT and MLCT, respectively) components in magnetic transition-metal compounds is discussed.

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Acknowledgements

The authors are deeply grateful to Fernand Spiegelman for his scientific openness, generous support, stimulating discussions and for his valuable friendship.

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  1. Laboratoire de Chimie Et Physique Quantiques, UMR 5626, Université de Toulouse 3, Paul Sabatier, 118 route de Narbonne, 31062, Toulouse, France

    Nicolas Suaud, Nadia Ben Amor, Nathalie Guihéry & Jean-Paul Malrieu

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  1. Nicolas Suaud
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  2. Nadia Ben Amor
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  4. Jean-Paul Malrieu
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Correspondence to Nathalie Guihéry.

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Suaud, N., Ben Amor, N., Guihéry, N. et al. Understanding the impact of correlation on bond length alternation in polyenes. Theor Chem Acc 140, 117 (2021). https://doi.org/10.1007/s00214-021-02769-2

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