A third-order nonlinear optical single crystal of 3,4-dimethoxy-substituted chalcone derivative with high laser damage threshold value: a potential material for optical power limiting

Abstract

Abstract Third-order nonlinear optical material 4-[(1 E )-3-(3,4-dimethoxyphenyl)-3-oxoprop-1-en-1-yl]phenyl 4-methylbenzene-1-sulfonate (DMPMS) is crystallized by slow solvent evaporation technique. The crystal has inversion symmetry and belongs to monoclinic system with $${P2}_{1}/c$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msub> <mml:mrow> <mml:mi>P</mml:mi> <mml:mn>2</mml:mn> </mml:mrow> <mml:mn>1</mml:mn> </mml:msub> <mml:mo>/</mml:mo> <mml:mi>c</mml:mi> </mml:mrow> </mml:math> space group. The C–H⋯O/C–H⋯π intermolecular interactions will be large complementarity for molecular density/crystal packing. A comprehensive investigation for absorbance and emission properties has been performed. Thermal stability is up to 258 °C without any weight loss and calculated value of laser damage threshold is ≈ 12 GW/cm 2 . The DMPMS shows low dielectric constant value, about 4.42 at 1 MHz and electronic polarizability values in the order of $${10}^{-23}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msup> <mml:mrow> <mml:mn>10</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>-</mml:mo> <mml:mn>23</mml:mn> </mml:mrow> </mml:msup> </mml:math> cm 3 . Furthermore, theoretical calculation has been performed using B3LYP and M06-2X functional. The static first-order hyperpolarizability parameter is 55 (B3LYP) and 34 (M06-2X) times that of urea. The total contribution of second-order hyperpolarizability is − 37.9 $$\times {10}^{-40 }\mathrm{esu}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mo>×</mml:mo> <mml:msup> <mml:mrow> <mml:mn>10</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>-</mml:mo> <mml:mn>40</mml:mn> </mml:mrow> </mml:msup> <mml:mi>esu</mml:mi> </mml:mrow> </mml:math> (in B3LYP functional) and − 25.77 $$\times {10}^{-40 }\mathrm{esu}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mo>×</mml:mo> <mml:msup> <mml:mrow> <mml:mn>10</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>-</mml:mo> <mml:mn>40</mml:mn> </mml:mrow> </mml:msup> <mml:mi>esu</mml:mi> </mml:mrow> </mml:math> (in M06-2X functional), respectively. Here, two-photon absorption mechanism is responsible for nonlinear absorption and co-efficient is found to be $$28.3 \times {10}^{-12}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mn>28.3</mml:mn> <mml:mo>×</mml:mo> <mml:msup> <mml:mrow> <mml:mn>10</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>-</mml:mo> <mml:mn>12</mml:mn> </mml:mrow> </mml:msup> </mml:mrow> </mml:math> m/W. In optical limiting study, limiting threshold is found to be 65 µJ. The real and imaginary third-order nonlinear optical susceptibility is of the order $${10}^{-12} \mathrm{esu}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msup> <mml:mrow> <mml:mn>10</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>-</mml:mo> <mml:mn>12</mml:mn> </mml:mrow> </mml:msup> <mml:mi>esu</mml:mi> </mml:mrow> </mml:math> .