The solvent effects on the linear and second-order nonlinear optical properties of an aminonaphtylethenylpyridinium (ANEP) dye are investigated by combining experimental and theoretical chemistry methods. On the one hand, deep near infrared (NIR) hyper-Rayleigh scattering (HRS) measurements (1840–1950 nm) are performed on solutions of di-8-ANEPPS in deuterated chloroform, dimethylformamide, and dimethylsulfoxide to determine their first hyperpolarizablity (βHRS). For the first time, these HRS experiments are carried out in the picosecond regime in the deep NIR with very moderate (≤3 mW) average input power, providing a good signal-to-noise ratio and avoiding solvent thermal effects. Moreover, the frequency dispersion of βHRS is investigated for Disperse Red 1 (DR1), a dye commonly used as HRS external reference. On the other hand, these are compared with computational chemistry results obtained by using a sequential molecular dynamics (MD) then quantum mechanics (QM) approach. The MD method allows accounting for the dynamical nature of the molecular structures. Then, the QM part is based on TDDFT/M06-2X/6-311+G* calculations using solvation models ranging from continuum to discrete ones. Measurements report a decrease of the βHRS of di-8-ANEPPS in more polar solvents and these effects are reproduced by the different solvation models. For di-8-ANEPPS and DR1, comparisons show that the use of a hybrid solvation model, combining the description of the solvent molecules around the probe by point charges with a continuum model, already achieves quasi quantitative agreement with experiment. These results are further improved by using a polarizable embedding that includes the atomic polarizabilities in the solvent description.
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7 November 2023
Research Article|
November 07 2023
First hyperpolarizability of the di-8-ANEPPS and DR1 nonlinear optical chromophores in solution. An experimental and multi-scale theoretical chemistry study
Charlotte Bouquiaux
;
Charlotte Bouquiaux
(Data curation, Formal analysis, Investigation, Methodology, Validation, Visualization, Writing – original draft)
1
University of Namur, Theoretical Chemistry Lab, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter
, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Pierre Beaujean
;
Pierre Beaujean
(Data curation, Formal analysis, Investigation, Methodology, Software, Validation, Visualization, Writing – review & editing)
1
University of Namur, Theoretical Chemistry Lab, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter
, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Tárcius N. Ramos
;
Tárcius N. Ramos
(Data curation, Formal analysis, Methodology, Software, Validation, Writing – review & editing)
1
University of Namur, Theoretical Chemistry Lab, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter
, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Frédéric Castet
;
Frédéric Castet
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Validation, Writing – review & editing)
2
University of Bordeaux, Institut des Sciences Moléculaires, UMR 5255 CNRS
, cours de la Libération 351, F-33405 Talence Cedex, France
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Vincent Rodriguez
;
Vincent Rodriguez
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Writing – original draft, Writing – review & editing)
2
University of Bordeaux, Institut des Sciences Moléculaires, UMR 5255 CNRS
, cours de la Libération 351, F-33405 Talence Cedex, France
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Benoît Champagne
Benoît Champagne
b)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Writing – original draft, Writing – review & editing)
1
University of Namur, Theoretical Chemistry Lab, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter
, rue de Bruxelles, 61, B-5000 Namur, Belgium
b)Author to whom correspondence should be addressed: benoit.champagne@unamur.be
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b)Author to whom correspondence should be addressed: benoit.champagne@unamur.be
J. Chem. Phys. 159, 174307 (2023)
Article history
Received:
September 04 2023
Accepted:
October 10 2023
Citation
Charlotte Bouquiaux, Pierre Beaujean, Tárcius N. Ramos, Frédéric Castet, Vincent Rodriguez, Benoît Champagne; First hyperpolarizability of the di-8-ANEPPS and DR1 nonlinear optical chromophores in solution. An experimental and multi-scale theoretical chemistry study. J. Chem. Phys. 7 November 2023; 159 (17): 174307. https://doi.org/10.1063/5.0174979
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