Vibrational spectra of vitreous germania from first-principles

We report on a first-principles investigation of the structural and vibrational properties of vitreous germania (v-GeO2). Our work focuses on a periodic model structure of 168 atoms, but three smaller models are also studied for comparison. We first carry out a detailed structural analysis both in real and reciprocal spaces. Our study comprises the partial pair correlation functions, the angular distributions, the total neutron correlation function, the neutron and x-ray total structure factors, and the Faber-Ziman and Bhatia-Thornthon partial structure factors. We find overall good agreement with available experimental data. We then obtain the vibrational frequencies and eigenmodes. We analyze the vibrational density of states in terms of Ge and O motions, and further in terms of rocking, bending, and stretching contributions. The inelastic neutron spectrum is found to differ only marginally from the vibrational density of states. Using a methodology based on the application of finite electric fields, we derive dynamical Born charge tensors and Raman coupling tensors. For the infrared spectra, we calculate the real and imaginary parts of the dielectric function, including the high-frequency and static dielectric constants. The Raman spectra are shown to be sensitive to the medium-range structure and support an average Ge-O-Ge angle of 135 degrees. We identify the shoulder X-2 as a signature of breathing O vibrations in three-membered rings. Four-membered rings are found to contribute to the main Raman peak. We advance an interpretation for the shoulder X-1 in terms of delocalized bond-bending modes. We derive bond polarizability parameters from the calculated Raman coupling tensors and demonstrate their level of reliability in reproducing the spectra. The calculated vibrational spectra all show good agreement with the respective experimental spectra.