Experimental and theoretical investigation of the firstorder hyperpolarizability of a class of triarylamine derivatives
Abstract
This paper reports on the static and dynamic firstorder hyperpolarizabilities of a class of pushpull octupolar triarylamine derivatives dissolved in toluene. We have combined hyperRayleigh scattering experiment and the coupled perturbed HartreeFock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) firstorder hyperpolarizability (β{sub HRS}) of nine triarylamine derivatives with distinct electronwithdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the firstorder hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solventinduced polarization and the frequency dispersion effect, the environment substantially affects the firstorder hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic firstorder hyperpolarizability of the derivatives. The firstorder hyperpolarizability of the derivatives was also modeled using the two and threelevel models, where the relationship between static and dynamic first hyperpolarizabilities is given bymore »
 Authors:
 Departamento de Ciências da Natureza, Matemática e Educação, Universidade Federal de São Carlos, Rod. Anhanguera–Km 174, 13600970 Araras, SP (Brazil)
 (Brazil)
 Instituto de Física de São Carlos, Universidade de São Paulo, Caixa Postal 369, 13560970 São Carlos, SP (Brazil)
 Instituto de Ciência de Tecnologia, Universidade Federal de Alfenas, Cidade Universitária  BR 267 Km 533, 37715400 Poços de Caldas, MG (Brazil)
 CEISAM–UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, 44322 Nantes (France)
 Instituto de Física, Universidade de São Paulo, CP 66318, 05314970 São Paulo, SP (Brazil)
 Publication Date:
 OSTI Identifier:
 22416113
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ARYLATION; DENSITY FUNCTIONAL METHOD; ELECTRONS; HARTREEFOCK METHOD; PERMITTIVITY; POLARIZATION; RAYLEIGH SCATTERING; SOLVENTS; TOLUENE
Citation Formats
Silva, Daniel L., Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Instituto de Física, Universidade de São Paulo, CP 66318, 05314970 São Paulo, SP, Fonseca, Ruben D., Mendonca, Cleber R., De Boni, Leonardo, Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Vivas, Marcelo G., Ishow, E., and Canuto, Sylvio. Experimental and theoretical investigation of the firstorder hyperpolarizability of a class of triarylamine derivatives. United States: N. p., 2015.
Web. doi:10.1063/1.4906893.
Silva, Daniel L., Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Instituto de Física, Universidade de São Paulo, CP 66318, 05314970 São Paulo, SP, Fonseca, Ruben D., Mendonca, Cleber R., De Boni, Leonardo, Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Vivas, Marcelo G., Ishow, E., & Canuto, Sylvio. Experimental and theoretical investigation of the firstorder hyperpolarizability of a class of triarylamine derivatives. United States. doi:10.1063/1.4906893.
Silva, Daniel L., Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Instituto de Física, Universidade de São Paulo, CP 66318, 05314970 São Paulo, SP, Fonseca, Ruben D., Mendonca, Cleber R., De Boni, Leonardo, Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br, Vivas, Marcelo G., Ishow, E., and Canuto, Sylvio. 2015.
"Experimental and theoretical investigation of the firstorder hyperpolarizability of a class of triarylamine derivatives". United States.
doi:10.1063/1.4906893.
@article{osti_22416113,
title = {Experimental and theoretical investigation of the firstorder hyperpolarizability of a class of triarylamine derivatives},
author = {Silva, Daniel L., Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br and Instituto de Física, Universidade de São Paulo, CP 66318, 05314970 São Paulo, SP and Fonseca, Ruben D. and Mendonca, Cleber R. and De Boni, Leonardo, Email: dlsilva.physics@gmail.com, Email: deboni@ifsc.usp.br and Vivas, Marcelo G. and Ishow, E. and Canuto, Sylvio},
abstractNote = {This paper reports on the static and dynamic firstorder hyperpolarizabilities of a class of pushpull octupolar triarylamine derivatives dissolved in toluene. We have combined hyperRayleigh scattering experiment and the coupled perturbed HartreeFock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) firstorder hyperpolarizability (β{sub HRS}) of nine triarylamine derivatives with distinct electronwithdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the firstorder hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solventinduced polarization and the frequency dispersion effect, the environment substantially affects the firstorder hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic firstorder hyperpolarizability of the derivatives. The firstorder hyperpolarizability of the derivatives was also modeled using the two and threelevel models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the twolevel model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped fewlevel model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.},
doi = {10.1063/1.4906893},
journal = {Journal of Chemical Physics},
number = 6,
volume = 142,
place = {United States},
year = 2015,
month = 2
}

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