Application of the time-dependent local density approximation to optical activity

Abstract

As part of a general study of the time-dependent local density approximation (TDLDA), we report here calculations of optical activity of chiral molecules, taking as examples methyloxirane and ${\mathrm{C}}_{76}.$ The theory automatically satisfies sum rules and the Kramers-Kronig relation between circular dichroism and optical rotatory power. It reproduces the absorption strengths of the strong states quite well and qualitatively describes the chiroptical properties; quantitatively, the predictions of the circular dichroism of the lowest states are a factor of 2–4 too high. In the chiral fullerene ${\mathrm{C}}_{76}$ the TDLDA provides a consistent description of the optical absorption spectrum, the circular dichroism spectrum, and the optical rotatory power, except for an overall shift of the theoretical spectrum.