Modeling and tuning the electronic, mechanical and optical properties of a recently synthesized 2D polyaramid: a first principles study.

This work delves into a methodology of modeling 2D materials and their structural engineering, considering an example of a recently synthesized 2D polyaramid (2DPA-1). A bottom-up approach similar to experimental techniques is implemented for modeling, and then its electronic structures and phonon spectrum and the quadratic nature of flexural phonons are analyzed. Furthermore, boron and nitrogen atoms are substituted for the carbon atom of the amide group of 2DPA-1, and their effects on its electronic properties, phonon spectrum, and mechanical properties are compared with those of pristine 2DPA-1 using density functional theory calculations. The molecular dynamics (AIMD) simulations validate the thermal stability of our system at high temperatures. The spin-polarized electronic structures reveal the transformation of pristine 2DPA-1 from a semiconductor to a half-metal and its magnetic behaviour upon nitrogen substitution. Constraining the quadratic nature of flexural phonons using the Born-Huang criteria significantly enhances the phonon spectra, leading to more accurate and reliable simulations. For modulated 2DPA-1, the elastic modulus varies between 17 and 27 N m, and the absorption peaks shift from ∼5.15 eV to 2.42 eV, enabling the application of polymeric 2D nanomaterials in photocatalysis and sensing, where light absorption in the near-infrared region is important. Finally, validation of our methodology is confirmed, as computed Young's modulus (11.26-11.76 GPa) of 2DPA-1 matches excellently with the experimental value (12.7 ± 3.8 GPa). Overall, this study reveals the modeling of a newly synthesized polymeric 2D material, and tuning its properties results in smaller bandgaps and half-metallic and magnetic behaviours.