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Empirical corrections in the G3X and G3X(CCSD) theories combined with a compact effective pseudopotential

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Abstract

The G3X-CEP and G3X(CCSD)-CEP composite methods were developed by combining a compact effective pseudopotential (CEP) with the G3X and G3X(CCSD) all-electron methods. The G3/05 test set was used as reference data to analyze the performance of these methods by calculating enthalpies of formation, ionization energies, electron affinities, proton affinities, and molecular atomization energies. Tests were carried out considering different numbers of higher-level correction (HLC) parameters as well as a scaling of the experimental atomization energies of the elements used to determine the enthalpies of formation. The overall behavior of G3X-CEP and G3X(CCSD)-CEP calculations considering six HLC parameters presented a mean absolute error around 1.15 kcal mol−1 for all calculated properties. This tendency is intermediate to the G3CEP and G4CEP methods. The use of scaled experimental atomization energies of the elements provided a mean absolute error around 1.11 kcal mol−1, which is similar to the one obtained by the G4CEP theory (1.09 kcal mol−1). The G3X-CEP and G3X(CCSD)-CEP enthalpies of formation were significantly improved with respect to experimental results. Molecular atomization energies showed a modest improvement, while the ionization energies and electronic affinities were slightly affected indirectly by the reoptimized HLC parameters. The proton affinities were nearly unaffected.

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Acknowledgements

The authors would like to acknowledge financial support from FAPEAM (Fundação de Amparo à Pesquisa do Estado do Amazonas), FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo-Center for Computational Engineering and Sciences, Grants 2013/08293-7 and 2017/11485-6), 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 access to their computational facilities.

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Authors and Affiliations

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

    Cleuton de Souza Silva & Rogério Custodio

  2. Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Campus de Itacoatiara, Itacoatiara, Amazonas, 69100-021, Brazil

    Cleuton de Souza Silva

Authors
  1. Cleuton de Souza Silva
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  2. Rogério Custodio
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Correspondence to Rogério Custodio.

Electronic supplementary material

Below is the link to the electronic supplementary material.

214_2018_2206_MOESM1_ESM.docx

The supplemental file contains truncated basis set (G3large—Table S.1, G3Xlarge—Table S.2), to be used along with the CEP pseudopotential. The file also contains the following calculated data using G3X-CEP, G3(CCSD)-CEP, EnAt1, and EnAt2 theories: enthalpies of formation—Table S.3, ionization energies—Table S.4, electron affinities—Table S.5, proton affinities—Table S.6, and atomization energies—Table S.7. (DOCX 111 kb)

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Silva, C.S., Custodio, R. Empirical corrections in the G3X and G3X(CCSD) theories combined with a compact effective pseudopotential. Theor Chem Acc 137, 24 (2018). https://doi.org/10.1007/s00214-018-2206-3

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