d⁶versus d¹⁰, Which Is Better for Second Harmonic Generation Susceptibility? A Case Study of K₂TGe₃Ch₈ (T = Fe, Cd;...

Two acentric chalcogenide compounds, K₂CdGe₃S₈ and K₂CdGe₃Se₈, were synthesized via conventional high-temperature solid-state reactions. The crystal structures of K₂CdGe₃S₈ and K₂CdGe₃Se₈ were accurately determined by single-crystal X-ray diffraction and crystallize in the K₂FeGe₃S₈ structure type. K₂CdGe₃S₈ is isostructural to K₂FeGe₃S₈ with superior nonlinear optical properties. For the second harmonic generation (SHG) response, K₂CdGe₃S₈ is 18× K₂FeGe₃S₈ for samples of particle size of 38-55 μm. The superior nonlinear optical properties of K₂CdGe₃S₈ over K₂FeGe₃S₈ are mainly contributed by the chemical characteristics of Cd compared with Fe, which are elucidated by nonlinear optical property measurements, electronic structure calculations, and density functional theory calculations. The [CdS₄] tetrahedra within K₂CdGe₃S₈ exhibit a higher degree of distortion and larger volume compared to the [FeS₄] tetrahedra in K₂FeGe₃S₈. This study possesses a good platform to investigate how d-block elements contribute to the SHG response. The fully occupied d¹⁰-elements are better for SHG susceptibility than d⁶-elements in this study. K₂CdGe₃S₈ is a good candidate as an infrared nonlinear optical material of high SHG response (2.1× AgGaS₂, samples of particle size of 200-250 μm), type-I phase-matching capability, high laser damage threshold (6.2× AgGaS₂), and good stability.