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A study of the rotational barriers for some organic compounds using the G3 and G3CEP theories

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Abstract

The G3, G3CEP, MP4, MP4CEP, QCISD(T), and QCISD(T)CEP methods were applied to study 43 internal rotational barriers of different molecules. The calculated G3 and G3CEP barriers were accurate with respect to those obtained experimentally, typically showing deviations of <0.50 kcal mol−1. The results for the MP4CEP, MP4, QCISD(T), and QCISD(T)CEP calculations were less accurate, and larger deviations of approximately ±1 kcal mol−1 were observed. The accuracy of G3CEP was comparable to that of G3, but a reduction in CPU time of between 5 and 35 % was observed when the dependence of the pseudopotentials on the size of the molecule and atom type was taken into account. The behaviors of the energy components show that these corrections depend on the molecular environment and whether the calculations are performed with all electrons or pseudopotentials. Usually, the predominance of a specific effect follows a distinct pattern when the G3 and G3CEP results are compared. For the G3 calculations, the most important component of the corrected MP4/6-31G(d) rotational energy is ΔE 2df,p. Among the 43 molecules, 29 were dependent on polarization effects, ΔE 2df,p; 19 were dependent on diffuse functions, ΔE +; and 13 depended on the effects of more elaborate basis functions (ΔE G3large). Similar behavior was observed for the G3CEP calculations: polarization effects were more important for 25 molecules, followed closely by the effect of diffuse functions for 23 molecules, and finally the effect of large basis sets (19 molecules). ΔE QCI correction seldom resulted in significant effects on the G3 and G3CEP calculations.

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Acknowledgments

We acknowledge financial support from FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo—Center for Computational Engineering and Sciences: grant 2013/08293-7), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), and FAEPEX-UNICAMP (Fundo de Apoio ao Ensino, à Pesquisa e à Extensão da UNICAMP). The National Center of High Performance Computing in São Paulo (CENAPAD—SP) is acknowledged for making their computational facilities available to us. We also would like to thank Dr. Telma Rie Doi Ducati for helpful comments and suggestions.

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Authors and Affiliations

  1. Instituto de Química, Universidade Estadual de Campinas, Barão Geraldo, 13083-970, Campinas, São Paulo, Brazil, P. O. Box 6154

    Douglas Henrique Pereira, Roberto Rittner & Rogério Custodio

  2. Departamento de Ciências Exatas e Biotecnológicas, Universidade Federal do Tocantins, Campus de Gurupi, 77410-530, Gurupi, Tocantins, Brazil

    Douglas Henrique Pereira

  3. Instituto de Química, Universidade de São Paulo, 05508-900, São Paulo, São Paulo, Brazil, P. O. Box 26077

    Lucas Colucci Ducati

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  1. Douglas Henrique Pereira
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  2. Lucas Colucci Ducati
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  3. Roberto Rittner
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  4. Rogério Custodio
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Corresponding author

Correspondence to Rogério Custodio.

Electronic supplementary material

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ESM 1

Figures S1–S23, depicting the experimental and theoretical barriers and respective energy components for the G3 and G3CEP calculations (Supplementary Information 1) (DOC 5854 kb)

ESM 2

Cartesian coordinates (in Å) of the optimized geometries calculated at the MP2(full)/6-31G(d) level of theory with specific dihedral bond angles for all molecules are provided (Supplementary Information 2) (DOC 1069 kb)

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Pereira, D.H., Ducati, L.C., Rittner, R. et al. A study of the rotational barriers for some organic compounds using the G3 and G3CEP theories. J Mol Model 20, 2199 (2014). https://doi.org/10.1007/s00894-014-2199-3

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  • DOI: https://doi.org/10.1007/s00894-014-2199-3

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