Electronic structure of SiO2: Charge redistribution contributions to the dynamic dipoles/effective charges of the infrared active normal modes

Abstract

This article applies ab initio calculations at the (i) Hartree–Fock self-consistent field single determinant and (ii) configuration interaction multideterminant expansion levels to study the diagonal components of the dynamic dipoles, Δμi/Δqj with i=j, or equivalently infrared effective charges, ei*, associated with asymmetric bond stretching νy, symmetric bond stretching νz, and out-of-plane bond rocking νx, normal mode infrared active vibrations of noncrystalline SiO2. The normal mode dynamic dipoles (hereafter, Δμ/qi) are decomposed into equilibrium charge density (ionic) and orbital variation (charge redistribution) contributions. The calculations are based on small clusters in which Si–O–Si groups are connected through O atoms to embedding Si atom terminators Si* that emulate the connectivity of these Si–O–Si groups to the SiO2 continuous random network. Values of Δμ/Δqi have been determined as a function of the Si–O–Si bond angle α at the bridging O-atom sites, and agree with values obtained from analysis of infrared spectra. Finally, the ab initio calculations are extended to noncrystalline silicon–carbon alloys and silicon nitride, and values of Δμ/Δqi are determined for infrared active vibrations associated with N- and C-atom asymmetric stretching normal mode motions. The normalized equilibrium charge density or ionic contributions of the O, N, and C atoms follow trends expected on the basis of their relative Pauling electronegativities in bonds with Si.