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On the origin of the barriers and the structures of acetaldehyde in its ground and first singlet excited state

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Summary

Anab initio study of the ground and the first singlet excited states of acetaldehyde has been performed to analyze the molecular properties as a function of the methyl torsion and the aldehydic hydrogen wagging angles. The structural characteristics and the conformational behaviour in both electronic states have been determined. The important structural changes between the two states have been analyzed by a decomposition of the total energy into its components. It was found that the methyl torsion barriers arise mainly from attractive interactions. Evidence is presented which shows that these barriers arise from in-plane and out-of-plane hyperconjugative effects involving the oxygen atom. It is also shown that the pyramidalization experienced by the carbonyl carbon in the first singlet excited state has two sources, namely, a decrease in the electronic repulsion and an increase in the electron-nucleus attraction.

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Authors and Affiliations

  1. Departamento de Informática, Universidad de Castilla-La Mancha, Ronda de Calatrava s/n, 13071, Ciudad Real, Spain

    C. Muñoz-Caro & A. Niño

  2. Department of Chemistry, Brock University, L2S3A1, St. Catharines, Ont., Canada

    D. C. Moule

Authors
  1. C. Muñoz-Caro
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  2. A. Niño
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  3. D. C. Moule
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Muñoz-Caro, C., Niño, A. & Moule, D.C. On the origin of the barriers and the structures of acetaldehyde in its ground and first singlet excited state. Theoret. Chim. Acta 88, 299–310 (1994). https://doi.org/10.1007/BF01113453

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  • DOI: https://doi.org/10.1007/BF01113453

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