Structural, electronic, and nonlinear optical properties of small silver clusters doped graphyne and pyrazine‐modified graphyne: A computational and comparative study

Abstract

The electronic and second‐order nonlinear optical (NLO) properties of small Agn clusters (n = 1 to 3) doped graphyne (GY) and pyrazine‐modified graphyne (pyGY) have been investigated employing (time‐dependent) density functional theory calculations. A large triangular hole of GY provides an efficient site to accommodate the Agn cluster, and an Ag atom prefers to be located in the center of the pyGY, interacting with the two pyridine N atoms. The silver clusters have strong interactions with GY/pyGY, and the intramolecular charge transfer is significant for determining NLO properties. The first hyperpolarizability (β0) values can be modulated by the introduction of silver clusters. The results show that the second‐order NLO response of Ag2/Ag3 doped pyGY complex is stronger than that of corresponding Ag2/Ag3 doped GY complex, while the β0 for single Ag doped GY is significantly higher than that of Ag@pyGY. Hence, the NLO responses of these complexes depend on the size of the clusters and the type of nanosheets. All complexes exhibit excellent transparency in the deep ultraviolet region, especially Ag3@GY/pyGY. These results suggest that these Agn clusters doped GY/pyGY are excellent candidates for potential applications in optical devices.