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A DFT analysis of electronic, reactivity, and NLO responses of a reactive orange dye: the role of Hartree-Fock exchange corrections

Fonseca, Sávio ; Santos, Lucas ; Pereira, Regina ; Modesto-Costa, Lucas ; da Cunha, Antônio R. ; Siqueira, Marcelo R. S. ; Carvalho, Francisco A. O. ; Andrade-Filho, Tarciso ; Gester, Rodrigo

Journal of molecular modeling, 2022-04, Vol.28 (4), p.85-85, Article 85 [Periódico revisado por pares]

Berlin/Heidelberg: Springer Berlin Heidelberg

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  • Título:
    A DFT analysis of electronic, reactivity, and NLO responses of a reactive orange dye: the role of Hartree-Fock exchange corrections
  • Autor: Fonseca, Sávio ; Santos, Lucas ; Pereira, Regina ; Modesto-Costa, Lucas ; da Cunha, Antônio R. ; Siqueira, Marcelo R. S. ; Carvalho, Francisco A. O. ; Andrade-Filho, Tarciso ; Gester, Rodrigo
  • Assuntos: Absorption spectra ; Characterization and Evaluation of Materials ; Chemistry ; Chemistry and Materials Science ; Chromophores ; Computer Appl. in Life Sciences ; Computer Applications in Chemistry ; Continuum modeling ; Dyes ; Hartree approximation ; Molecular Medicine ; Nucleophiles ; Optical properties ; Refractivity ; Review ; Solvation ; Solvent effect ; Solvents ; Theoretical and Computational Chemistry
  • É parte de: Journal of molecular modeling, 2022-04, Vol.28 (4), p.85-85, Article 85
  • Notas: ObjectType-Article-2
    SourceType-Scholarly Journals-1
    ObjectType-Feature-3
    content type line 23
    ObjectType-Review-1
  • Descrição: An experimental and theoretical study based on DFT/TD-DFT approximations is presented to understand the nature of electronic excitations, reactivity, and nonlinear optical (NLO) properties of reactive orange 16 dye (RO16), an azo chromophore widely used in textile and pharmacological industries. The results show that the solvent has a considerable influence on the electronic properties of the material. According to experimental results, the absorption spectrum is formed by four intense transitions, which have been identified as π → π ∗ states using TD-DFT calculations. However, the TD-DFT results reveal a weak n → π ∗ in the low-lying spectral region. Continuum models of solvation indicate that these states suffer from bathochromic (ca. 15 nm) and hypsochromic shifts (ca. 4 nm), respectively. However, the expected blue shift for the absorption n → π ∗ is only described using long-range or dispersion-corrected DFT methods. RO16 is classified as a strong electrophilic system, with electrophilicity ω > 1.5 eV. Concerning the nucleophilicity parameter ( N ), from vacuum to solvent, the environment is active and changes the nucleophilic status from strong to moderate nucleophile (2.0 ≤ N ≤ 3.0 eV). The results also suggest that all electrical constants are strongly dependent on long-range and Hartree-Fock exchange contributions, and the absence of these interactions gives results far from reality. In particular, the results for the NLO response show that the chromophore presents a potential application in this field with a low refractive index and first hyperpolarizability ca. 214 times bigger than the value usually reported for urea ( β = 0.34 × 10 − 30 esu), which is a standard NLO material. Concerning the solvent effects, the results indicate that the polarizability increases ∼ 20 × 1 0 − 24 esu from gas to solvent while the first hyperpolarizability is calculated as ∼ 45 × 1 0 − 30 esu, ca. 180%, regarding the vacuum. The results suggest RO16 is a potential compound in NLO applications. Graphical Abstract The frontier molecular orbitals, and the inverse relation between the energy-gap ( E gap ) and the first hyperpolarizability (β)
  • Editor: Berlin/Heidelberg: Springer Berlin Heidelberg
  • Idioma: Inglês
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