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Two-Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two-Photon Absorption Spectrum of Reichardt’s Dye

Authors

  • Małgorzata Wielgus,

    1. Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50370 Wrocław (Poland)
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  • Dr. Robert Zaleśny,

    1. Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50370 Wrocław (Poland)
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  • Dr. N. Arul Murugan,

    1. Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, 10691 Stockholm (Sweden)
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  • Prof. Jacob Kongsted,

    1. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M (Denmark)
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  • Prof. Hans Ågren,

    1. Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, 10691 Stockholm (Sweden)
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  • Prof. Marek Samoc,

    1. Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50370 Wrocław (Poland)
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  • Prof. Wojciech Bartkowiak

    Corresponding author
    1. Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50370 Wrocław (Poland)
    • Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50370 Wrocław (Poland)

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Abstract

In this study, we report on the influence of solvent on the two-photon absorption (2PA) spectra of Reichardt’s dye (RD). The measurement of 2PA cross-sections is performed for three solvents (chloroform, dimethyl formamide, and dimethyl sulfoxide) using the Z-scan technique. The key finding of this study is the observation that the cross-section, corresponding to the 2PA of the intramolecular charge-transfer state, diminishes substantially upon increasing the solvent polarity. To unravel the solvent dependence of the 2PA cross-section, the electronic structure of RD is determined using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach, in which polarization between the solute and solvent is taken into account by using a self-consistent scheme in the solvent polarization. The two-state approximation proves to be adequate for the studied system, and allowed the observed solvent-polarity-induced decrease of the 2PA cross-section to be related to the decrease of the transition moment and the increase in the excitation energy.

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