Structural, electronic and optical properties of monoclinic Na2Ti3O7 from density functional theory calculations: A comparison with XRD and optical absorption measurements

Abstract

Powder samples of bulk monoclinic sodium trititanate Na2Ti3O7 were prepared carefully by solid state reaction, and its monoclinic P21/m crystal structure and morphology were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM), respectively. Moreover, the sodium trititanate main energy band gap was estimated as Eg=3.51±0.01eV employing UV–Vis spectroscopy, which is smaller than the measured 3.70eV energy gap published previously by other authors. Aiming to achieve a better understanding of the experimental data, density functional theory (DFT) computations were performed within the local density and generalized gradient approximations (LDA and GGA, respectively) taking into account dispersion effects through the scheme of Tkatchenko and Scheffler (GGA+TS). Optimal lattice parameters, with deviations relative to measurements Δa=−0.06Å, Δb=0.02Å, and Δc=−0.09Å, were obtained at the GGA level, which was then used to simulate the sodium trititanate electronic and optical properties. Indirect band transitions have led to a theoretical gap energy value of about 3.25eV. Our results, however, differ from pioneer DFT results with respect to the specific Brillouin zone vectors for which the indirect transition with smallest energy value occurs. Effective masses for electrons and holes were also estimated along a set of directions in reciprocal space. Lastly, our calculations revealed a relatively large degree of optical isotropy for the Na2Ti3O7 optical absorption and complex dielectric function.