Growth, Characterization and Theoretical Study of a Novel Organometallic Nonlinear Optical Crystal: CdHg(SCN)4(C2H5NO)2

A novel potentially useful second harmonic generation (SHG) organometallic nonlinear optical (NLO) crystal: cadmium mercury thiocyanate bis(N-methylformamide), CdHg(SCN)₄(C₂H₅NO)₂ (CMTN), has been prepared, and large high-optical-quality single crystals with dimensions up to 30 ×27×9 mm³ have been grown by the temperature-lowering method. Its structural, physicochemical and optical properties are characterized by elemental analyses, X-ray powder diffraction, Fourier transform infrared and Raman spectroscopy, thermal analysis, powder SHG measurements and UV/Vis/NIR transmission. The specific heat has been determined to be 515.5 J?mol^?1?K^?1 at 300 K. CMTN possesses good physicochemical stability up to 128.5^°C, exhibits powder SHG efficiencies 0.8 times that of urea and its UV transparency cutoff is 358 nm. By the use of the DFT/B3LYP/6-31G(d) method, the microscopic second order NLO behavior of CMTN has been investigated by computing the first-order hyperpolarizability together with that of CdHg(SCN)₄ (CMTC) and CdHg(SCN)₄(C₃H₈O₂) (CMTG) crystals. The results have been explained based on their crystal structures.