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Synthesis, characterization and third-order nonlinear optical properties of polydiacetylene nanostructures, silver nanoparticles and polydiacetylene–silver nanocomposites

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Abstract

We have synthesized, characterized and studied the third-order nonlinear optical properties of two different nanostructures of polydiacetylene (PDA), PDA nanocrystals and PDA nanovesicles, along with silver nanoparticles-decorated PDA nanovesicles. The second molecular hyperpolarizability γ(−ω; ω, −ω, ω) of the samples has been investigated by antiresonant ring interferometric nonlinear spectroscopic (ARINS) technique using femtosecond mode-locked Ti:sapphire laser in the spectral range of 720–820 nm. The observed spectral dispersion of γ has been explained in the framework of three-essential states model and a correlation between the electronic structure and optical nonlinearity of the samples has been established. The energy of two-photon state, transition dipole moments and linewidth of the transitions have been estimated. We have observed that the nonlinear optical properties of PDA nanocrystals and nanovesicles are different because of the influence of chain coupling effects facilitated by the chain packing geometry of the monomers. On the other hand, our investigation reveals that the spectral dispersion characteristic of γ for silver nanoparticles-coated PDA nanovesicles is qualitatively similar to that observed for the uncoated PDA nanovesicles but bears no resemblance to that observed in silver nanoparticles. The presence of silver nanoparticles increases the γ values of the coated nanovesicles slightly as compared to that of the uncoated nanovesicles, suggesting a definite but weak coupling between the free electrons of the metal nanoparticles and π electrons of the polymer in the composite system. Our comparative studies show that the arrangement of polymer chains in polydiacetylene nanocrystals is more favourable for higher nonlinearity.

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Acknowledgement

The corresponding author acknowledges the financial support for this research work by the University Grants Commission (UGC), Government of India (CSIR-UGC Research Fellowship, F. No. 2-44 /2000(i)-EU II dated 1.2.2001).

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BHUSHAN, B., TALWAR, S.S., KUNDU, T. et al. Synthesis, characterization and third-order nonlinear optical properties of polydiacetylene nanostructures, silver nanoparticles and polydiacetylene–silver nanocomposites. Pramana - J Phys 87, 56 (2016). https://doi.org/10.1007/s12043-016-1264-0

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