Exploring the Reliability of DFT Calculations of the Infrared and Terahertz Spectra of Sodium Peroxodisulfate

Abstract

A number of DFT programs with various combinations of pseudo-potentials and van der Waals’ dispersive corrections have been used to optimize the structure of sodium peroxodisulfate, Na2(SO4)2, and to calculate the infrared, attenuated total reflectance and terahertz absorption spectra of the powdered crystal. Comparison of the results from the different methods highlights the problems of calculating the absorption spectrum reliably. In particular the low frequency phonon modes are especially sensitive to the choice of grids to represent the wavefunction or the charge distribution, k-point integration grid and the energy cutoff. A comparison is made between the Maxwell-Garnett (MG) and Bruggeman effective medium methods used to account for the effect of crystal shape on the predicted spectrum. Possible scattering of light by air inclusions in the sample and by larger particles of Na2(SO4)2 is also considered using the Mie method. The results of the calculations are compared with experimental measurements of the transmission and attenuated total reflection spectra.