Ab initio study for superior sensitivity of graphyne nanoflake towards nitrogen halides over ammonia.

Graphyne (GYN) has received immense attention in gas adsorption applications due to its large surface area. The adsorption of toxic ammonia and nitrogen halides gaseous molecules on graphyne has been theoretically studied at ωB97XD/6-31 + G(d, p) level of DFT. The counterpoise corrected interaction energies of NH 3 , NF 3 , NCl 3 , and NBr 3 molecules with GYN are - 4.73, - 2.27, - 5.22, and - 7.19 kcal mol -1 , respectively. Symmetry-adapted perturbation theory (SAPT0) and noncovalent interaction index (NCI) reveal that the noncovalent interaction between analytes and GYN is dominated by dispersion forces. The significant change in electronic behavior, i.e., energies of HOMO and LUMO orbitals and NBO charge transfer correspond to the pronounced sensitivity of GYN towards considered analytes, especially NBr 3 . Finally, TD-DFT calculation reveals a decrease in electronic transition energies and shifting of adsorption to a longer wavelength. The recovery time for NX 3 @GYN is observed in nanoseconds, which is many orders of magnitude smaller than the reported systems. The recovery time is further decreased with increasing temperature, indicating that the GYN benefits from a short recovery time as a chemical sensor.