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The lithium–thiophene interaction: a critical study using highly correlated electronic structure approaches of quantum chemistry

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Abstract

The fundamental multicentric interaction of a lithium atom with a single thiophene ring is addressed. A systematic study of the interaction energy (IE) and geometry for the Li–T charge-transfer complex is done at the MP2 and CCSD(T) levels using increasingly large basis sets up to aug-cc-pVQZ (AVQZ). Basis set superposition errors (BSSE) are evaluated and shown to have a major impact on the value of the IE. The Fixed-Node Diffusion Monte Carlo (FN-DMC) method is used as an alternative basis-set-free approach to obtain what is likely to be the most accurate estimate of the IE obtained so far. While counterpoise-corrected MP2/AVQZ and CCSD(T)/AVTZ interaction energies are found to be −3.8 and −7.5 kcal/mol, the FN-DMC method yields +1.3 ± 1.7 kcal/mol. The slow convergence of the ab initio IE (and some key structural parameters) with respect to basis set quality and the discrepancy with the FN-DMC result is discussed. A visualization of the electron pairing using the electron pair localization function (EPLF) for the Li-doped versus undoped thiophene is also presented.

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Notes

  1. To give an idea of the computational resources required with the largest basis set, the MP2/AVQZ optimization of LiT used more than 150 GB of disk space, 27 GB of RAM and took 5 days on 8 processors starting from the MP2/AVTZ optimized geometry.

  2. The CCSD(T)/AVTZ calculations for LiT already involve about 1.5 × 107 CSF.

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Acknowledgments

M. Caffarel and A. Scemama would like to thank IDRIS (CNRS, Orsay), CCRT (CEA/DAM, Ile-de-France), CALMIP (Université de Toulouse) for computational support. A. Ramírez-Solís wishes to thank the FOMES2000 “Cómputo Científico” Project for CPU time on the IBM-p690 supercomputer.

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Authors and Affiliations

  1. Laboratoire de Chimie et Physique Quantiques, CNRS-IRSAMC Université de Toulouse, Toulouse, France

    Michel Caffarel & Anthony Scemama

  2. Depto. de Física, Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Cuernavaca, 62209, Morelos, Mexico

    Alejandro Ramírez-Solís

Authors
  1. Michel Caffarel
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  2. Anthony Scemama
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  3. Alejandro Ramírez-Solís
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Correspondence to Alejandro Ramírez-Solís.

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Dedicated to the memory of Professor Jean-Pierre Daudey and published as part of the Daudey Memorial Issue.

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Caffarel, M., Scemama, A. & Ramírez-Solís, A. The lithium–thiophene interaction: a critical study using highly correlated electronic structure approaches of quantum chemistry. Theor Chem Acc 126, 275–287 (2010). https://doi.org/10.1007/s00214-009-0713-y

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