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A global analysis of excited states: the global transition contribution grids

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Abstract

In this work, we develop and apply a tool allowing for a condensed analysis of the nature and energetics of the electronic excited states computed using time-dependent density functional theory (TD-DFT) inspired by the transition contribution map (TCM) analysis of Hakkinen and collaborators. This new analysis will be referred to as Global Transition Contribution Grid (G_TCG) and will be applied to compare the behavior of two families of exchange correlation functionals for the description of the excited states of a series of five polycyclic aromatic hydrocarbons (PAH) molecules. These latter are indeed known to be problematically described at the excited state by local and semi-local exchange correlation functionals. Although further improvement is possible, our results show that G_TCG can be used to qualitatively spot difference in the behavior of the different functionals not only in energetics but also in the nature of the computed transitions in a condensed and qualitative way. More generally, the global grid-based analysis could help in the analysis of the excited states of systems possessing a complex electronic structure and a dense molecular orbitals manifold close to the frontier orbitals, such as nanoparticles or large π-conjugated systems, for which several hole–electron pairs are expected to contribute to single electronic transitions.

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Acknowledgements

C. M. and I.C. thank the European Research Council (ERC) for funding under the European Union’s Horizon 2020 research and innovation program (Grant agreement No 648558, STRIGES CoG grant).

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Authors and Affiliations

  1. Institute of Chemistry for Life and Health Sciences, Chemical Theory and Modelling Group, Chimie ParisTech, PSL University, CNRS, 75005, Paris, France

    C. Morgillo, F.-A. Korsaye, A. Ottochian, C. Adamo & I. Ciofini

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  1. C. Morgillo
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  2. F.-A. Korsaye
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  3. A. Ottochian
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  4. C. Adamo
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  5. I. Ciofini
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Correspondence to C. Adamo or I. Ciofini.

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Morgillo, C., Korsaye, FA., Ottochian, A. et al. A global analysis of excited states: the global transition contribution grids. Theor Chem Acc 140, 158 (2021). https://doi.org/10.1007/s00214-021-02854-6

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