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Methylenecyclopropene: local vision of the first 1B2 excited state

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Abstract

The 1A1 ground and the first 1B2 excited states of the methylenecyclopropene (triafulvene) are described by localized wave functions, based on 20 structures valence bond structures. The results are compared to CASSCF(4,4) calculations for both the energetics and the dipole moment. Additional calculations with partial electronic delocalization are presented, and it is shown that the dipole moment modification does not correspond to a situation where the antiaromatic situation prevails (with 4n electrons in the cycle). Part of the analysis uses a “trust factor” that helps to decide if a wave function is appropriate to describe a given state. The trust factor compares the VB wave function to the CASSCF’s with their overlap. Finally, the valence bond density is used to produce density maps that illustrate the electron transfer upon excitation.

A projector-based method compares CASSCF wave functions to local wave functions, including Lewis structures as shown in the picture. A “trust factor” (τ) is obtained. Both the ground state and the first excited state of the methylenecyclopropene are discussed

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Acknowledgements

Professor Wei Wu at Xiamen University is gratefully acknowledged for the XMVB code. The authors also acknowledge Dr. Tognetti and Pr. Christophe Morell for the access to the Descriptor algorithm to integrate the density differences.

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Authors and Affiliations

  1. Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France

    Julien Racine & Stéphane Humbel

  2. Université Tahar Moulay de Saida, Laboratoire de Modélisation et de Méthodes de Calcul, BP 138 cité ENNASR, 20000, Saida, Algérie

    Mohamed Abdelhak Touadjine & Ali Rahmouni

Authors
  1. Julien Racine
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  2. Mohamed Abdelhak Touadjine
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  3. Ali Rahmouni
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  4. Stéphane Humbel
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Correspondence to Stéphane Humbel.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

Annexes

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Table 6

Table 6 Experimental C2v geometry of the methylenecyclopropene[a] used for all calculations [21]
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Table 7

Table 7 Coefficients obtained in the valence bond computation (20 structures)
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Racine, J., Touadjine, M.A., Rahmouni, A. et al. Methylenecyclopropene: local vision of the first 1B2 excited state. J Mol Model 23, 22 (2017). https://doi.org/10.1007/s00894-016-3191-x

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  • DOI: https://doi.org/10.1007/s00894-016-3191-x

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