Artículo
Modulation of the NLO properties of p-coumaric acid by the solvent effects and proton dissociation
Damasceno, Marcus V.A.; Cunha, Antônio R.; Provasi, Patricio Federico
; Pagola, Gabriel Ignacio
; Siqueira, Marcelo; Manzoni, Vinícius; Gester, Rodrigo; Canuto, Sylvio
Fecha de publicación:
11/2023
Editorial:
Elsevier Science
Revista:
Journal of Molecular Liquids
ISSN:
0167-7322
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Solute-solvent interactions and deprotonation effects have been related to second-order nonlinear optical response modulators. This work takes advantage of sequential Monte Carlo/Quantum mechanics together with Time-Dependent Density Functional Theory, Coupled Cluster methods, and the hyper-Rayleigh scattering formalism to investigate how these effects influence the stability and optical response of p-coumaric acid (pCA) and its anionic and diionic forms. The solvent influences the chromophores in different ways, inducing bathochromic and hypsochromic solvatochromism so for the neutral pCA molecule as for its deprotonated derivatives. The results indicate a high sensitivity of the nonlinear optics (NLO) parameters with relation to proton dissociation. Ionization of the carboxyl group produces the lowest values of the first frequency-dependent hyperpolarizability (βHRS), while phenolic deprotonation leads to the highest values. The results show that proton removal can be used as a switch that modulates the NLO response within a wide range of values (159.15≤βHRS≤4393.97 au) greater than those reported for reference NLO chromophores like urea (37.3 au) and p-nitroaniline (74.3 au). Thermochemical analysis of enthalpies and Gibbs free energies indicate that both monoionic forms of the pCA molecule are the most stable in gas or water solvents. Furthermore, these structures represent the limits of NLO modulation in the gas and solvent phases. Analysis of the projected density of states and mapping of the molecular electrostatic potential indicate that increased contributions from conduction electrons found in the aromatic ring are the mechanism by which deprotonation enhances the NLO response. All the results show that ionic pCA forms are promising in the functionalization of optoelectronic devices.
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Articulos(IFIBA)
Articulos de INST.DE FISICA DE BUENOS AIRES
Articulos de INST.DE FISICA DE BUENOS AIRES
Articulos(IMIT)
Articulos de INST.DE MODELADO E INNOVACION TECNOLOGICA
Articulos de INST.DE MODELADO E INNOVACION TECNOLOGICA
Citación
Damasceno, Marcus V.A.; Cunha, Antônio R.; Provasi, Patricio Federico; Pagola, Gabriel Ignacio; Siqueira, Marcelo; et al.; Modulation of the NLO properties of p-coumaric acid by the solvent effects and proton dissociation; Elsevier Science; Journal of Molecular Liquids; 394; 123587; 11-2023; 1-18
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