First molecular electronic hyperpolarizability of series of π-conjugated oxazole dyes in solution: an experimental and theoretical study

Abegão, Luis M. G.; Fonseca, Ruben D.; Santos, Francisco A.; Rodrigues, José J.; Kamada, Kei; Mendonça, Cleber Renato; Piguel, Sandrine; Boni, Leonardo De

doi:10.1039/c9ra05246a

Cited by 20 publications

(15 citation statements)

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“…From comparison with the theoretical and experimental results, a good agreement was observed for the dynamic first molecular hyperpolarizability, in particular when it is taken into account the experimental error (20%) in HRS measurement. In fact, the comparison between the measured βHRS values of the studied compounds with similar ones reported previously, such as chalcones derivatives [28], oxazoles dyes [29], and dibenzylideneacetones derivatives with different substituents [49], reveals the potential of using the current compounds as frequency converters. For example, the reported βHRS value of a compound from the same molecular structure family (1E,4E)-1,5-bis(4-bromophenyl)penta-1,4-dien-3-one was 25 × 10 −30 •cm 4 •statvolt −1 [49], which is, two times lower than the value obtained for the 4-DMDBA.…”

Section: First Molecular Hyperpolarizabilitysupporting

confidence: 74%

“…For example, the reported βHRS value of a compound from the same molecular structure family (1E,4E)-1,5-bis(4-bromophenyl)penta-1,4-dien-3-one was 25 × 10 −30 •cm 4 •statvolt −1 [49], which is, two times lower than the value obtained for the 4-DMDBA. Another example, an oxazole derivative 4-((5-phenyloxazol-2-yl)ethynyl)benzonitrile [29], with a longer π-electron backbone length presented a value of 45 × 10 −30 •cm 4 •statvolt −1 , which still is lower than the 4-DMDBA.…”

Section: First Molecular Hyperpolarizabilitymentioning

confidence: 96%

“…A 532 nm narrow bandpass filter, with a 10 nm bandwidth, was used to make sure that only the SHG signal to be detected by the PMT. More details about the experimental setup can be found elsewhere [27][28][29].…”

Section: Optical Measurementsmentioning

confidence: 99%

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Nonlinear Optical Study in a Set of Dibenzylideneacetone Derivatives with Potential for Optical Frequency Conversion

et al. 2020

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The search for advanced optical materials, in particular, materials with nonlinear optical responses, has, in the last years, experienced substantial growth due to their vast applications in the photonics field. One of those applications is ultra-fast optical frequency conversion, in the optics communications field. Organic compounds have emerged as promising candidates for raw materials to develop nonlinear optical devices, such as optical converters, due to their intrinsic ultra-fast electronic responses. Also, the easy tailoring of organic molecular structures makes organic materials much more appealing than the inorganic ones. In this work, we have performed a linear and nonlinear optical characterization of a set of dibenzylideneacetone derivatives. The nonlinear optical responses investigated correspond to second- and third-order nonlinear processes, namely, first electronic molecular hyperpolarizability and two-photon absorption cross-section, respectively. The value of the first electronic molecular hyperpolarizability, up to 52 cm4·statvolt−1, could be considered a robust value when compared to the short-sized π-electron backbone length of the studied compounds. Such results suggest that these compounds exhibit the potential to be used as optical frequency converters. Quantum chemical calculations were used to predict the theoretical value of the first molecular hyperpolarizability, as well as to simulate the one- and two-photon absorption spectra for all compounds.

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Section: First Molecular Hyperpolarizabilitysupporting

confidence: 74%

Section: First Molecular Hyperpolarizabilitymentioning

confidence: 96%

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Nonlinear Optical Study in a Set of Dibenzylideneacetone Derivatives with Potential for Optical Frequency Conversion

et al. 2020

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“…Calculations of the static and dynamic (λ = 1064 nm) NLO responses were performed at the TDDFT/M06-2X/6-311+G* level using the Gaussian16 package . The M06-2X , functional exhibits an excellent general performance, and in the case of the calculation of first hyperpolarizabilities, its predictions are in good agreement with experiment and/or with higher-level (wave function) methods thanks to its high percentage of exact Hartree–Fock exchange. − We focused in this work on the hyper-Rayleigh scattering (HRS) response, β HRS , and the associated depolarization ratio (DR), which are associated respectively with the second harmonic light intensity and to the symmetry of the molecular scatterer. Full expressions of these terms can be found in ref .…”

Section: Computational and Theoretical Methodsmentioning

confidence: 99%

Unravelling the Effects of Cholesterol on the Second-Order Nonlinear Optical Responses of Di-8-ANEPPS Dye Embedded in Phosphatidylcholine Lipid Bilayers

2021

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Cholesterol is known for its role in maintaining the correct fluidity and rigidity of the animals cell membranes and thus their functions. Assessing the content and the role of cholesterol in lipid bilayers is therefore of crucial importance for a deeper understanding and control of membrane functioning. In this computational work, we investigate bilayers built from three types of glycerophospholipid phosphatidylcholine (PC) lipids, namely dipalmitoylphosphatidylcholine (DPPC), 1-palmitoyl-2-oleoyl-snglycero-3-phosphocholine (POPC), and dioleoylphosphatidylcholine (DOPC), and containing different amounts of cholesterol by analyzing the second-harmonic generation (SHG) nonlinear optical (NLO) response of a probe molecule, di-8-ANEPPS, inserted into the membranes. This molecular property presents the advantage to be specific to interfacial regions such as lipid bilayers. To unravel these effects, Molecular Dynamics (MD) simulations have been performed on both DPPC and DOPC lipids by varying the cholesterol mole fraction (from 0 to 0.66), while POPC was only considered as a pure bilayer. In the case of the structural properties of the bilayers, all the analyses converge toward the same conclusion: as the mole fraction of cholesterol increases, the systems become more rigid, confirming the condensing effect of cholesterol. In addition, the chromophore is progressively more aligned with respect to the normal to the bilayer. On the contrary, addition of unsaturation disorders the lipid bilayers, with barely no impact on the alignment of the chromophore. Then, using the frames obtained from the MD simulations, the first hyperpolarizability β of the dye in its environment has been computed at the TDDFT level. On the one hand, the addition of cholesterol induces a progressive increase of the diagonal component the β tensor parallel to the bilayer normal. On the other hand, larger β values have been calculated for the unsaturated than for the saturated lipid systems. In summary, this study illustrates the relationship between the composition and structure of the bilayers and the NLO responses of the embedded dye.

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“…Several experimental and theoretical works have contributed to these goals. For example, the effect of π−conjugation, [16][17][18] bond-length alternation, [19][20][21] and solvent 22,23 have been explored experimentally and/or theoretically.…”

Section: Introductionmentioning

confidence: 99%

A generalized few-state model for the first hyperpolarizability

Alam

Beerepoot

Ruud

2020

The Journal of Chemical Physics

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The properties of molecules depend on their chemical structure and thus structure-property relations help design molecules with desired properties. Few-state models are often used to interpret experimental observations of nonlinear optical properties. Not only the magnitude, but also the relative orientation of the transition dipole moment vectors is needed for few-state models of the non-linear optical properties. The effect of the relative orientation of the transition dipole moment vectors is called dipole alignment and this effect has previously been studied for multiphoton absorption properties. However, so far no such studies are reported for the first hyperpolarizability. Here we present a generalized few-state model for the static and dynamic first hyperpolarizability β , accounting for the effect of dipole alignment. The formulae derived in this work are general in the sense that they can be used for any few-state model, i.e. two-state model, three-state model or in general an n-state model. Based on the formulae, we formulate minimization and maximization criteria for the alignment of transition dipole moment vectors. We demonstrate the importance of dipole alignment by applying the formulae to the static first hyperpolarizability of ortho-, metaand para-nitroaniline. The formulae and the analysis provide new ways to understand structure-property relationship for β and can hence be used to fine-tune the magnitude of β in a molecule.

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First molecular electronic hyperpolarizability of series of π-conjugated oxazole dyes in solution: an experimental and theoretical study

Abstract: In this work, we report for the first time, the experimental and theoretical first molecular electronic hyperpolarizability of eleven π-conjugated oxazoles compounds in toluene medium, by using the hyper-Rayleigh scattering (HRS) technique.

Cited by 20 publications

References 44 publications

Nonlinear Optical Study in a Set of Dibenzylideneacetone Derivatives with Potential for Optical Frequency Conversion

Nonlinear Optical Study in a Set of Dibenzylideneacetone Derivatives with Potential for Optical Frequency Conversion

Unravelling the Effects of Cholesterol on the Second-Order Nonlinear Optical Responses of Di-8-ANEPPS Dye Embedded in Phosphatidylcholine Lipid Bilayers

A generalized few-state model for the first hyperpolarizability

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