Theoretical Investigation of Structural, Electronic and Optical Properties of Cs3MoO4(HCO3) with NLO Active Functional Units

Abstract Employing functional building units with microscopic second‐order NLO response has been proposed to explore high performance NLO materials. Herein, structural, electronic and optical properties of non‐centrosymmetric molybdenyl carbonate Cs 3 MoO 4 (HCO 3 ) with NLO active functional units have been examined based on density functional theory. Theoretical results are consistent with experimentally mentioned data, confirming the reliable method. Detailed geometric structure, electronic attributes, linear optical properties, and nonlinear optical properties of Cs 3 MoO 4 (HCO 3 ) are provided. Analysis of structures, compositions of bands and plots of charge density suggest that asymmetric functional building units [MoO 4 ] and [HCO 3 ] exhibit varying degrees of second‐order Jahn‐Teller distortions, and therefore have a significant impact on the electronic structure and optical properties of Cs 3 MoO 4 (HCO 3 ). Maximum absolute value of SHG coefficients at 1064 nm is 0.671 pm/V for d 15 , which is nearly twice as much as that of KDP. Further researches are needed in future to validate and enhance optical anisotropy characteristic of Cs 3 MoO 4 (HCO 3 ) for satisfying the phase matching conditions. Analysis results indicate that microscopic origins of SHG response in Cs 3 MoO 4 (HCO 3 ) are complicated, such as geometric environment, induced polar asymmetric functional building units, and electronic properties. Continuous research on structure‐property relationship of NLO materials is needed for exploring more competitive NLO materials.