Dispersion effects inSiO2polymorphs: Anab initiostudy

Abstract

The effect of electronic dispersion over a wide variety of SiO2 polymorphs (faujasite, ferrierite, α-cristobalite, α-quartz, coesite, and stishovite) is investigated using state-of-the-art density functional theory. Different functionals and dispersion correction schemes are compared, ranging from the local density approximation to fully nonlocal exchange-correlation functionals. It is shown that both empirical dispersion corrections and fully nonlocal functionals improve the energetics and give correct volumetric data. However, the correct volume results come from error cancellation between an overestimation of the Si-O distance and an underestimation of the Si-O-Si angle. Quantum Monte Carlo is used to compute the quartz-cristobalite energy difference within an accuracy of 0.2 kCal/mol per SiO2 unit. This demonstrates the feasability of achieving subchemical accuracy on extended systems, and confirms the validity of the Slater-Jastrow ansatz for describing SiO2 polymorphs.