Carbonatoperoxovanadates with Strong Second‐Harmonic Generation: Insights from First‐Principles Calculations on Anisotropic Structures and Optical Parameters

Abstract Carbonatoperoxovanadates are considered as promising functional materials in optoelectronic devices due to their excellent optical properties, particularly strong second‐harmonic generation (SHG) response. However, the relationship between their geometric structures and optical properties remains unclear. Herein, the structural, electronic, and optical properties of carbonatoperoxovanadates A 3 VO(O 2 ) 2 CO 3 (A=K, Rb, and Cs) were investigated using first‐principles calculation. Results suggest that high‐density and parallel arrangement of nonlinear optical active [VO(O 2 ) 2 CO 3 ] units are conducive to generating large SHG response in A 3 [V(O 2 ) 2 O]CO 3 . Optical anisotropy was observed. Birefringence values for A 3 [V(O 2 ) 2 O]CO 3 were comparable to those of commonly used infrared nonlinear optical materials. Specifically, results of tiny optical characteristics (local dipole moments, HUMO‐LUMO gap, polarizability anisotropy, and hyperpolarizability) indicate that asymmetry [VO(O 2 ) 2 CO 3 ] is an excellent nonlinear optical active functional unit, owing to the synergistic effect between its non‐centrosymmetric nonlinear optical elements. This study elucidates the structure‐property relationship of carbonatoperoxovanadates, offering valuable insights for designing novel high‐performance SHG materials.