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Infrared intensities of \((B_{6}C)^{2-}\): a true challenge for DFT methods

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Abstract

Absolute infrared intensities of \((B_{6}C)^{2-}\) were evaluated with a great variety of DFT and ab initio methods and basis sets. It is shown that the intensities calculated by different levels of theory may not agree with each other even in the qualitative (weak/strong) sense. Geometrical parameters, as well as net atomic charges evaluated from multiple partition schemes, did not vary as much as the intensities and thus cannot explain the tremendous differences found for the latter. As there are no experimental estimates for the intensities to guide the theoretical evaluation, deciding on the best level of theory is reduced to comparisons between the different DFT methods and QCISD or CCSD, believed to be the best theoretical estimates in the set. The differences found among the various DFT methods suggest the development of new methods, instead of converging to a focal point, is rather diverging.

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Data availability

Vibrational frequencies, bond lengths and atomic charges (Hirshfeld, CM5, CHELPG, NPA, ADCH, Mulliken, APT and DDEC6) for all the levels of theory tested here. The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Code availability

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Funding

WER received financial support to computational facilities from Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico (FAADCT/PR). LJD received a doctoral fellowship (2017/22741–3) from Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP).

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Authors and Affiliations

  1. Department of Chemistry, Federal University of Technology – Paraná [UTFPR], 84.017–220, Ponta Grossa, PR, Brazil

    Wagner E. Richter

  2. Institute of Chemistry, State University of Campinas [UNICAMP], 13.083–970, Campinas, SP, Brazil

    Leonardo J. Duarte

Authors
  1. Wagner E. Richter
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  2. Leonardo J. Duarte
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Contributions

Data collection and analysis were performed by Wagner Eduardo Richter. Figures were obtained by Leonardo José Duarte using his personal computer code. The first draft of the manuscript was written by Wagner Eduardo Richter and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Wagner E. Richter.

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The authors declare no competing interests.

Additional information

This article belongs to the Topical Collection: XXI-Brazilian Symposium of Theoretical Chemistry (SBQT2021)

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Supplementary file 1 (pdf 6997 KB)

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Richter, W.E., Duarte, L.J. Infrared intensities of \((B_{6}C)^{2-}\): a true challenge for DFT methods. J Mol Model 28, 301 (2022). https://doi.org/10.1007/s00894-022-05275-9

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