Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials

Two novel mixed-alkali-metal selenate nonlinear-optical (NLO) crystals, Na₃Li(H₂O)₃(SeO₄)₂·3H₂O (I) and CsLi₃(H₂O)(SeO₄)₂ (II), have been successfully synthesized by an aqueous solution evaporation method. Both compounds feature the unique layers constructed of the same functional moieties including SeO₄ and LiO₄ tetrahedra: [Li(H₂O)₃(SeO₄)₂·3H₂O]_∞^3- layers in I and [Li₃(H₂O)(SeO₄)₂]_∞^- layers in II. The titled compounds display wide optical band gaps of 5.62 and 5.66 eV, respectively, according to the UV-vis spectra. Interestingly, they exhibit significantly different second-order nonlinear coefficients (0.34 × KDP and 0.70 × KDP, respectively). Detailed dipole moment calculations manifest that the large disparity can be attributed to the difference in the dipole moment of the crystallographically independent SeO₄ and LiO₄ groups. This work confirms that alkali-metal selenate system is an excellent candidate for short-wave ultraviolet NLO materials.