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Electronic spectroscopy of a solvatochromic dye in water: comparison of static cluster/implicit and dynamical/explicit solvent models on structures and energies

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Abstract

In this study, we analyze the photophysics of the N-methyl-6-oxyquinolinium betaine (MQ) solvatochromic dye in aqueous solution, focussing on the important structural rearrangement of its first solvation shell following the electronic excitation, which is characterized by a strong charge transfer. To this aim, we compare the results provided by ground- and excited-state ab-initio molecular dynamics with that of full QM calculations on clusters including a small number of solvent molecules (from 1 to 4), taking into account bulk solvent effects by the Polarizable Continuum Model. The two methods agree in predicting that while in the ground electronic state between three and four water molecules are strongly coordinated to the oxygen atom of MQ, in the excited state two water molecules are present in the first solvation layer of the MQ oxygen. Vertical excitation and emission energies computed on the structures provided by the two approaches allow for estimates of the Stokes shift consistent with the experimental results. On the ground of the present results, some general considerations on the advantages and limitations of the dynamical and static approaches in describing a photoactivated process in solution are proposed.

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Acknowledgements

The support of MIUR (FIRB ‘Futuro in Ricerca’ prot. RBFR10Y5VW, PRIN2009 prot. 2009PRAM8L, PRIN 2010-2011 prot. 2010ERFKXL) is acknowledged. JC acknowledges ‘Fundación Ramón Areces’ for funding his postdoctoral position, and the Pisa Unit of ICCOM-CNR Pisa for hospitality. FA acknowledges support from the Marie Curie COFUND program U-Mobility, co-financed by the University of Malaga, the European Commission FP7 under GA No. 246550 and Ministerio de Economiá y Competitividad (COFUND201340259). AP, GD and NR thank Gaussian Inc. (Wallingford, CT) for financial support.

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Author notes

  1. Alessio Petrone

    Present address: Department of Chemistry, University of Washington, Seattle, WA, 98195, USA

Authors and Affiliations

  1. Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), CNR–Consiglio Nazionale delle Ricerche, UOS di Pisa, Area della Ricerca, via G. Moruzzi 1, 56124, Pisa, Italy

    Javier Cerezo, Francisco J. Avila Ferrer & Fabrizio Santoro

  2. Dipartimento di Scienze Chimiche, Università di Napoli `Federico II’, Complesso Universitario di M.S.Angelo, via Cintia, 80126, Naples, Italy

    Alessio Petrone, Greta Donati & Nadia Rega

  3. Physical Chemistry, Faculty of Science, University of Málaga, Málaga, 29071, Spain

    Francisco J. Avila Ferrer

  4. CNR–Consiglio Nazionale delle Ricerche, Istituto di Biostrutture e Bioimmagini (IBB-CNR), via Mezzocannone 16, 80136, Naples, Italy

    Roberto Improta

  5. IIT@CRIB Center for Advanced Biomaterials for Healthcare, Largo Barsanti e Matteucci, Italian Institute of Technology, 80125, Naples, Italy

    Nadia Rega

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  1. Javier Cerezo
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Corresponding authors

Correspondence to Fabrizio Santoro, Roberto Improta or Nadia Rega.

Additional information

Javier Cerezo and Alessio Petrone contributed equally to the work.

Published as part of the special collection of articles “Charge Transfer Modeling in Chemistry”.

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Cerezo, J., Petrone, A., Ferrer, F.J.A. et al. Electronic spectroscopy of a solvatochromic dye in water: comparison of static cluster/implicit and dynamical/explicit solvent models on structures and energies. Theor Chem Acc 135, 263 (2016). https://doi.org/10.1007/s00214-016-2009-3

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