RbMo2P3O14 with large birefringence mainly induced by highly distorted [MoO6] in uncommon [Mo2P3O14]∞ layers

Abstract

The introduction of d⁰ transition metal Mo⁶⁺ cations into a phosphate generates a new acentric molybdophosphate, RbMo₂P₃O₁₄. It shows uncommon [Mo₂P₃O₁₄]_∞ layers composed of isolated [MoO₆] octahedra and [P₃O₁₀] groups. To the best of our acknowledge, it exhibits the largest birefringence (a calculated value of 0.166 at 546 nm) among reported molybdophosphates. In addition, it also possesses a shorter UV cut-off edge (about 250 nm) than other molybdates and molybdophosphates, indicating that it can be used as a birefringent crystal in the UV optical region. First-principles electronic structure analysis suggests that the large birefringence mainly originates from highly distorted [MoO₆].