Exploration of the structure, electronic and optical properties of AB ₂(PO₃)₅ polyphosphates: a first-principle approach

Abstract The density functional theory method was applied using the gradient PBE, incorporating the hybrid PBE0 functional along with dispersion corrections D3(BJ). These objectives were accomplished through the utilization of the CRYSTAL package, employing a localized atomic orbital basis. Calculations encompassing crystal properties, including electronic, structural, and linear/nonlinear opto-electronic characteristics, were conducted for monoclinic AB 2 (PO 3 ) 5 . Specifically, the polyphosphates investigated in this study are RbPb 2 (PO 3 ) 5 , CsPb 2 (PO 3 ) 5 , KBa 2 (PO 3 ) 5 , and RbBa 2 (PO 3 ) 5 . It was demonstrated that in monoclinic phosphates, phosphorus and oxygen atoms form infinite chains [PO4] ∞ based on the· <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mo>⋯</mml:mo> </mml:math> O1-P-O1 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mo>⋯</mml:mo> </mml:math> ·structure. Alkali metal and lead (barium) atoms are surrounded by oxygen atoms O2, forming polyhedra. Infrared absorption spectra calculations confirmed the presence of chain backbone structural units. Additionally, band structure and partial density of electronic states were determined. The nature of valence and unoccupied states was also investigated. In lead-doped compounds, lead atoms contribute to the formation of upper-valence and lower-unoccupied states. Conversely, in barium-doped compounds, the upper valence states are primarily formed by O2 p -states, while the lower unoccupied states are formed by phosphorus. Also, the coefficients of second harmonic generation and birefringence were calculated, assessing the potential use of phosphates as nonlinear optical materials.