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Accurate atomic electron affinities calculated by using anionic Gaussian basis sets

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Abstract

The computation of accurate electron affinity (EA) remains one of the most difficult tasks in quantum chemistry. A major source of error in EA calculations is the inadequacy of the basis set (BS) to represent the anionic system, since the Gaussian exponents are normally optimized for the neutral atom energy. To overcome this problem, one must augment the BSs with diffuse functions, which allow a better description of long-range interactions in anionic systems. Here, we report a new methodology to generate BSs for accurate EA computation that consists in the direct optimization of the Gaussian exponents in an anionic environment. By using the anionic basis sets (ABSs), we substantially reduce the errors in EA calculation for boron, carbon, oxygen and fluorine. A graphical analysis of the ABS parameters shows that their exponents are able to span important regions for short- and long-ranged interactions, which permit the ABSs to properly describe both neutral and anionic systems.

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Acknowledgements

This study was financed in part by the Brazilian Agencies: The Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES; Grant No. 001) and The National Council of Scientific and Technological Development (CNPq). The calculations performed here made use of the computational resources of the Center of Mathematical Sciences Applied to Industry (CeMEAI) funded by FAPESP (Grant 2013/07375-0). Conselho Nacional de Desenvolvimento Científico e Tecnológico (Grant Nos. 001, 001).

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Authors and Affiliations

  1. Departamento de Química e Física Molecular, Instituto de Química de São Carlos, Universidade de São Paulo, 780, São Carlos, SP, 13560-970, Brazil

    Rafael Costa-Amaral, Ana C. M. Tello & Albérico Borges Ferreira da Silva

  2. Instituto de Química, Universidade Federal de Uberlândia, Uberlândia, Minas Gerais, 38408-100, Brazil

    Moacyr Comar Jr.

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  1. Rafael Costa-Amaral
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  2. Ana C. M. Tello
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  3. Moacyr Comar Jr.
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  4. Albérico Borges Ferreira da Silva
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Correspondence to Albérico Borges Ferreira da Silva.

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Costa-Amaral, R., Tello, A.C.M., Comar, M. et al. Accurate atomic electron affinities calculated by using anionic Gaussian basis sets. Theor Chem Acc 139, 128 (2020). https://doi.org/10.1007/s00214-020-02629-5

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