Molecular structure, linear and nonlinear optical properties of some cyclic phosphazenes: A theoretical investigation

• Theoretical structural results were compared with the experimental X-ray results.
• Vibrational and electronic contributions to (hyper) polarizabilities are calculated using HF, and DFT functionals.
• Reasonably-sized basis sets are used to give ‘high quality’ polarizabilities.

We report ab initio and density functional theory calculations of structural data, dipole moment, diagonal vibrational and electronic contributions to polarizability, vibrational and electronic contributions to first hyperpolarizability of some cyclic phosphazenes. The electronic structure of substituted cyclic phosphazenes has been investigated using Hartree-Fock and density functional theory. The vibrational and electronic contributions to polarizabilities and first hyperpolarizability of these molecules were calculated with HF method, and different DFT levels used the traditional B3LYP and PBE functional and the long-range corrected functional like Coulomb-attenuating method CAM-B3LYP, LC-BLYP and wB97XD used different basis sets. These cyclic phosphazenes adopts a planar structure. The chosen level of theory was found to describe satisfactory the molecular structure (r. m. s. of the relative deviations). The study reveals that the cyclic phosphazenes derivatives have large vibrational contribution to static first hyperpolarizability values. The results obtained from this work will provide into the electronic properties of this important class of inorganic polymers.

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