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A quantum chemical investigation of the electronic structure of thionine

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Abstract

We have examined the electronic and molecular structure of 3,7-diaminophenothiazin-5-ium dye (thionine) in the electronic ground state and in the lowest excited states. The electronic structure was calculated using a combination of density functional theory and multi-reference configuration interaction (DFT/MRCI). Equilibrium geometries were optimized employing (time-dependent) density functional theory (B3LYP functional) combined with the TZVP basis set. Solvent effects were estimated using the COSMO model and micro-hydration with up to five explicit water molecules. Our calculated electronic energies are in good agreement with experimental data. We find the lowest excited singlet and triplet states at the ground state geometry to be of π→π* (S1, S2, T1, T2) and n→π* (S3, T3) character. This order changes when the molecular structure in the electronically excited states is relaxed. Geometry relaxation has almost no effect on the energy of the S1 and T1 states (∼0.02 eV). The relaxation effects on the energies of S2 and T2 are moderate (0.14–0.20 eV). The very small emission energy results in a very low fluorescence rate. While we were not able to locate the energetic minimum of the S3 state, we found a non-planar minimum for the T3 state with an energy which is very close to the energy of the S1 minimum in the gas phase (0.04 eV above). When hydration effects are taken into account, the n→π* states S3 and T3 are strongly blueshifted (0.33 and 0.46 eV), while the π→π* states are only slightly affected (<0.06 eV).

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Authors and Affiliations

  1. Grupo de Bioquímica Teórica, Universidad Industrial de Santander, Carrera 27, Calle 9, Bucaramanga, Colombia

    Angela Rodriguez-Serrano, Martha C. Daza & Markus Doerr

  2. Facultad de Química Ambiental, Universidad Santo Tomás, Carrera 18 No. 9-27, Bucaramanga, Colombia

    Markus Doerr

  3. Institute of Theoretical and Computational Chemistry, Heinrich Heine University of Düsseldorf, Universitätsstr. 1, D-40225, Düsseldorf, Germany

    Christel M. Marian

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  1. Angela Rodriguez-Serrano
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  2. Martha C. Daza
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  3. Markus Doerr
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Correspondence to Martha C. Daza or Markus Doerr.

Additional information

Electronic supplementary information (ESI) available: DFT/MRCI energies of the low-lying states along a linearly-interpolated path between the S0 and S1 geometries (Fig. 1); frontier Kohn-Sham BHLYP/ TZVP molecular orbitals computed at the T3 (n→π*) state minimum (Fig. 2); selected geometrical parameters of the thionine ground state calculated with the B3LYP functional and the TZVP, TZVPP and TZVP+R basis sets (Table 1); vertical singlet and triplet excitation energies ΔE (eV) of thionine calculated using the TZVP+R and the TZVP basis sets (Table 2); DFT/MRCI energies (ΔE), oscillator strengths (f(L)) and dominant contributions (DC) for each of the linearly interpolated geometries between the S1 and the S2 minima calculated at the DFT/MRCI/ TZVP level (Table 3); geometries and vibrational frequencies of the ground and excited states are provided as molden files: S0.molden, S1.molden, S2.molden, T1.molden, T2.molden and T3.molden. See DOI: 10.1039/c1pp05267e

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Rodriguez-Serrano, A., Daza, M.C., Doerr, M. et al. A quantum chemical investigation of the electronic structure of thionine. Photochem Photobiol Sci 11, 397–408 (2012). https://doi.org/10.1039/c1pp05267e

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