Optical activity of solids with many-body effects from first principles

First-principles theories of optical activity in crystalline solids have recently been developed [1-8]. For independent electrons within the framework of density functional theory (DFT), the calculated optical rotatory dispersion of tellurium shows excellent agreement with experiment [6]. However, for systems like quartz, local field effects have been found to be of crucial importance [4, 7-8]. Accurate optical rotatory power with local field effects for quartz was obtained by using either sum-over-states formulation [4,7] or linear response theory [4, 8] at the static limit. In this work, we extend the multipole formulation of the optical activity for solids from the independent particle picture to account for the many-body effects within the GW approximation plus Bethe-Salpeter Equation (BSE) framework. The GW approximation corrects the band gap as underestimated by DFT due to the self-interaction error. Together with the direct Coulomb term of the BSE kernel, we obtain the accurate optical gap which is crucial to calculate the optical activity and usually be treated as empirical parameter to be tuned in alignment with experiments. In addition, the exchange term of the BSE kernel is responsible for the local field effects [9]. Altogether, within the GW-BSE framework and the multipole formulation, the optical rotatory dispersion can be calculated accurately. We benchmarked our formulation with quartz and found good agreement with experiments.

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9. Rev. Mod. Phys. 74, 601-659 (2002).