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Relativistic four-component MRCISD+Q calculations of the six lowest valence states of molecular \(\text {I}_{2}^{-}\) anion including breit interactions

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Abstract

Context and results

This study aimed to obtain potential energy curves within a multireference 4-component relativistic method and to present spectroscopic constants (R\(_e\),\(\omega _{e}\),\(\omega _{e}\)x\(_e\),\(\omega _{e}\)y\(_e\), D\(_e\), D\(_0\), B\(_e\),\(\alpha _{e}\),\(\beta _{e}\),\(\gamma _{e}\) ), accurate extended Rydberg analytical form, and rovibrational levels for the 6 low-lying states of the I\(_2^{-}\) anion. For these states, some spectroscopic constants, rovibrational levels, and an accurate analytical form are presented for the first time in literature, and they are of interest for femtosecond and dynamics experiments of I\(_2^{-}\) as well as for electron attachment of I\(_2\). This study suggests that the inclusion of relativistic and correlation effects treated at the MRCISD+Q level is needed to obtain reliable results, specially for D\(_e\).

Computational and theoretical techniques

The potential energy curves of the ground and the excited states of the molecular iodine anion (I\(_2^{-}\)) were investigated at multireference configuration interaction (MRCISD) with Davidson size-extensivity correction (denoted as +Q) within a fully relativistic four-component relativistic framework including Breit interaction.

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All data generated or analyzed during this study were included in this published article.

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Acknowledgements

This work was supported by Universidade Federal de São João del Rei (CCO/UFSJ). YCCV thanks Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) for his PIBIC scholarship. LGMM thanks Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) for financial support under grant 408085/2021-5. RG also thanks the CNPQ and FAPDF for financial support.

Funding

This work was funded by Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) (grant 408085/2021-5).

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Authors and Affiliations

  1. Campus Centro Oeste Dona Lindu, Universidade Federal de São João Del Rei, Rua Sebastião Gonçalves Coelho, 400, Divinópolis, 35501-296, Minas Gerais, Brasil

    Luiz Guilherme Machado de Macedo & Yasmin Celen de Castro Vieira

  2. Instituto Federal de Educação, Ciência e Tecnologia do Maranhão, Av. João Alberto, 1840, Bacabal, 65700-000, Maranhão, Brasil

    Rhuiago Mendes de Oliveira

  3. Instituto de Física, Universidade de Brasília, P.O. Box 04455, Brasília, 70919-970, Distrito Federal, Brasil

    Ricardo Gargano

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  1. Luiz Guilherme Machado de Macedo
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  2. Yasmin Celen de Castro Vieira
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  4. Ricardo Gargano
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Contributions

Ricardo Gargano (RG) and Luiz Guilherme Machado de Macedo (LGMM) contributed to the study’s conception. All authors contributed to the investigation. Yasmin Celen de Castro Vieira (YCCV) prepared all the figures. Rhuiago Mendes de Oliveira prepared the Rydberg fitting. The first draft of the manuscript was written by Luiz Guilherme Machado de Macedo (LGMM). Ricardo Gargano (RG) and Luiz Guilherme Machado de Macedo (LGMM) were responsable for funding acquisition and resources. The review and editing of the final form of the manuscript were made by Ricardo Gargano (RG) and Luiz Guilherme Machado de Macedo (LGMM). All authors have read and approved the final manuscript.

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Correspondence to Luiz Guilherme Machado de Macedo.

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Yasmin Celen de Castro Vieira, Rhuiago Mendes de Oliveira and Ricardo contributed equally to this work

This paper belongs to the Topical Collection IX Symposium on Electronic Structure and Molecular Dynamics - IX SeedMol.

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de Macedo, L.G.M., de Castro Vieira, Y.C., de Oliveira, R.M. et al. Relativistic four-component MRCISD+Q calculations of the six lowest valence states of molecular \(\text {I}_{2}^{-}\) anion including breit interactions. J Mol Model 29, 207 (2023). https://doi.org/10.1007/s00894-023-05564-x

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