Polysulfide Anions [S x ] 2− ( x = 2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials

Abstract Infrared nonlinear optical (IR NLO) materials play significant roles in laser technology. The novel functional building units (FBUs) are of great importance in constructing NLO materials with strong second harmonic generation (SHG). Herein, polysulfide anion [S x ] 2− (x = 2, 3, 4, 5) units are investigated on NLO‐related properties and structure‐performance relationships. Theoretical calculations uncover that the [S x ] 2− (x = 2, 3, 4, 5) units are potential IR NLO FBUs with large polarizability anisotropy ( δ ), hyperpolarizability ( β ) and wide HOMO–LUMO gap. Fourteen crystals including [S x ] 2− (x = 2, 3, 4, 5) units are calculated and analyzed. The results show that these units can result in a wide IR transmittance range, significant SHG effects, wide band gap E g (Na 2 S 4 : E g = 3.09 eV), and large birefringence Δ n [BaS 3 ( P 2 1 2 1 2): Δ n = 0.70]. More importantly, it is highlighted that the crystal materials including with [S x ] 2− (x = 2, 3, 4, 5) groups are good candidates for the exploration of the outstanding IR NLO materials.