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Charge transfer excitations and constrained density functional theory

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Abstract

Making use of the initial and final Fukui functions approximated by the charge density of the initial (occupied) orbital and the final (unoccupied in the ground state) orbital to identify the charge transfer excitations in a time-dependent density functional theory calculation, and the acceptance and donation regions, we analyze the performance of constrained density functional theory to predict the excitation energies by considering several alternatives to fix the amount of charge transferred. It is shown that charge transfer excitations energies may be accurately determined through this approach when one fixes the final charge in the acceptance region to a value that complements the net charge already present to minus one.

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Acknowledgements

We thank the Laboratorio Nacional de Cómputo de Alto Desempeño for the use of their facilities through the Laboratorio de Supercómputo y Visualización of Universidad Autónoma Metropolitana-Iztapalapa. We also thank Conacyt for grant sinergia 1561802.

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Authors and Affiliations

  1. Departamento de Química, CONACYT-Universidad Autónoma Metropolitana–Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

    Javier Carmona-Espíndola

  2. Departamento de Química, Universidad Autónoma Metropolitana–Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

    José L. Gázquez

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  1. Javier Carmona-Espíndola
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  2. José L. Gázquez
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Correspondence to Javier Carmona-Espíndola or José L. Gázquez.

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Carmona-Espíndola, J., Gázquez, J.L. Charge transfer excitations and constrained density functional theory. Theor Chem Acc 141, 1 (2022). https://doi.org/10.1007/s00214-021-02860-8

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