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Dual fluorescence of 4-(dimethylamino)-pyridine: a comparative linear response TDDFT versus state-specific CASSCF study including solvent with the PCM model

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Abstract

Two different theoretical approaches have been used for the description of the experimentally observed dual luminescence of 4-(dimethylamino)pyridine (DMAP), introducing solvent effects with the polarizable continuum model (PCM), which seems needed to represent the dual fluorescence in polar media. These approaches are the linear response time-dependent density functional theory (TDDFT) and the state-specific complete active space self-consistent field. Both levels of theory represent the expected planar high-energy and the twisted intramolecular charge transfer (ICT) low-energy excited-state structures in the presence of solvent (toluene and acetonitrile). The comparison between both approaches shows that the main distortion of the ICT state is similar for both cases, i.e. twisting to almost 90º of the pyridine ring and the dimethylamino planes, but that other secondary distortions are slightly different. In the case of the TDDFT approach, the geometry optimizations of DMAP in the ground and excited states have been carried out using the conventional linear response approach (LR-PCM) for the solvent inclusion. The LR-PCM and the specific state (SS-PCM) approaches have been used for the prediction of the excitation and emission energies of DMAP in toluene and acetonitrile. The prediction of the emission energies at TDDFT/LR-PCM and CASPT2/PCM (complete active space perturbation theory) levels agrees with the experimental ones.

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Notes

  1. The computation of conical intersections under the CASSCF framework is not available using the PCM in our available software. The CI points are approximated as state averaged optimizations in S1.

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Acknowledgments

The D.G.I.(MEC)/FEDER (CTQ2013-48635-C2-2-P and CTQ2011-24800) projects are acknowledged for financial support. E. Manso thanks the MINECO for a FPU grant. We thank the Centro de Supercomputación de Galicia (CESGA) for computational resources.

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Authors and Affiliations

  1. Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, Complejo Científico-Tecnológico, 26004, Logroño, Spain

    José M. López-de-Luzuriaga, Elena Manso, Miguel Monge & Diego Sampedro

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  1. José M. López-de-Luzuriaga
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  2. Elena Manso
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  3. Miguel Monge
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  4. Diego Sampedro
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Correspondence to José M. López-de-Luzuriaga.

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214_2015_1659_MOESM1_ESM.docx

Table S1 displays the experimental and calculated (TDDFT and CASSCF) main distances for DMAP in the ground (S0) and lowest singlet excited states HE and LE both in the gas phase or introducing the solvents toluene and acetonitrile using the PCM model. The xyz coordinates of the fully optimized computed structures for the critical points for DMAP in the gas phase, toluene, and acetonitrile. TD-DFT electronic excitations in toluene and acetonitrile using LR-PCM and SS-PCM approaches (DOCX 42 kb)

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López-de-Luzuriaga, J.M., Manso, E., Monge, M. et al. Dual fluorescence of 4-(dimethylamino)-pyridine: a comparative linear response TDDFT versus state-specific CASSCF study including solvent with the PCM model. Theor Chem Acc 134, 55 (2015). https://doi.org/10.1007/s00214-015-1659-x

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