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Low-lying electronic excitations of a water-soluble BODIPY: from the gas phase to the solvated molecule

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Abstract

We present a description of the optical properties of a water-soluble BODIPY derivative in the gas phase and in water. Comparison with a hydrophobic BODIPY derivative with very similar structure but deprived of the hydrophilic groups, clarifies the effects of functionalization. The changes in solution are studied at different levels of modeling. In particular, we make use of Car–Parrinello molecular dynamics to take thermal motion into account, by generating a set of molecular configurations at about room temperature and embedding them in the polarizable continuum model (PCM) for the solvent. The theoretical scheme is that of time-dependent density functional theory which we apply using different approximations for the exchange-correlation functionals. Changes in the low-lying excitation spectrum (≈2.5–4.5 eV) of the solvated molecule in water relative to gas phase are shown to be due not only to the electrostatic interaction with the solvent but also to the thermal motion that induces a downward energy shift and broadening of the absorption lines. Addition of explicit water molecules to the PCM only affects spectral features at higher energies.

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Notes

  1. Note that the same analysis of broadening and shift of energy and oscillator strength could have been carried out in terms of the derivatives of \(\Delta E_i\) and \(f_i\) with respect to Cartesian displacements of atoms, without resorting to normal modes [60]. The translation between the two pictures is based on the following relation:

    $$\begin{aligned} \mid \frac{\partial \Delta E_k}{\partial \delta _j}\mid =\mid \sum _{i=1}^{N_a} \mathbf{k}^{(j)}_i \frac{\partial \Delta E_k}{\partial \mathbf{R}_i} \mid \end{aligned}$$
    (6)

    The usage of vibrational eigenvalues and eigenvectors greatly eases the computation of equilibrium values.

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Acknowledgements

Part of the computer resources were granted by CADMOS and the BG/Q project at the Swiss Federal Institute of Technology in Lausanne (EPFL). The financial support for CADMOS and the Blue Gene/Q system is provided by the Canton of Geneva, Canton of Vaud, Hans Wilsdorf Foundation, Louis-Jeantet Foundation, University of Geneva, University of Lausanne and the Swiss Federal Institute of Technology in Lausanne.

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Author notes

  1. Fabio Trani

    Present address: Department of Physical Sciences, University of Naples Federico II, 80126, Naples, Italy

Authors and Affiliations

  1. Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy

    Franco Egidi & Vincenzo Barone

  2. Institute of Theoretical Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland

    Fabio Trani & Wanda Andreoni

  3. CompuNet, Istituto Italiano di Tecnologia (IIT), 16163, Genova, Italy

    Pietro A. Ballone & Wanda Andreoni

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  1. Franco Egidi
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Correspondence to Wanda Andreoni.

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Egidi, F., Trani, F., Ballone, P.A. et al. Low-lying electronic excitations of a water-soluble BODIPY: from the gas phase to the solvated molecule. Theor Chem Acc 135, 264 (2016). https://doi.org/10.1007/s00214-016-2011-9

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