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Analysis of crystal field effects and interactions using X-ray restrained ELMOs

Abstract : The purpose of this study is to assess the capability of X-ray restrained molecular wavefunction methods to reproduce the perturbation due to the crystal field. The effect of the crystal environment on the molecular charge densities has been thoroughly investigated experimentally and theoretically. However, the same analysis in terms of molecular orbitals is unprecedented. We specifically analysed the extremely localized molecular orbitals (ELMOs) because they allow for a valence bond like interpretation that is closer to the typical chemical reasoning. For a set of test molecules, we calculated first principles wavefunctions (called primary wavefunctions) and the corresponding scattered intensities (primary structure factors), that we afterwards used for X-ray restrained Hartree-Fock and ELMO calculations. This mimics the typical procedure of modelling wavefunctions from experimental X-ray diffraction, having the primary wavefunction as benchmark. This study follows a previous investigation concerning the effects of electron correlation, where it was shown that those subtle features could be retrieved only to a minor extent. The electric field generated by surrounding molecules is instead more substantial. Therefore, retrieving this information should be more successful and, in case, extremely useful for supramolecular chemistry and crystal engineering. The work also provides useful indications to experimentalists who want to exploit the potentialities offered by the X-ray restrained wavefunction methods.
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https://hal.univ-lorraine.fr/hal-02495246
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Submitted on : Thursday, May 28, 2020 - 5:06:50 PM
Last modification on : Monday, December 14, 2020 - 5:32:15 PM

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Michelle Ernst, Alessandro Genoni, Piero Macchi. Analysis of crystal field effects and interactions using X-ray restrained ELMOs. Journal of Molecular Structure, Elsevier, 2020, pp.127975. ⟨10.1016/j.molstruc.2020.127975⟩. ⟨hal-02495246⟩

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