Chiroptical properties from time-dependent density functional theory. I. Circular dichroism spectra of organic molecules

Abstract

We report the implementation of the computation of rotatory strengths, based on time-dependent density functional theory, within the Amsterdam Density Functional program. The code is applied to the simulation of circular dichroism spectra of small and moderately sized organic molecules, such as oxiranes, aziridines, cyclohexanone derivatives, and helicenes. Results agree favorably with experimental data, and with theoretical results for molecules that have been previously investigated by other authors. The efficient algorithms allow for the simulation of CD spectra of rather large molecules at a reasonable accuracy based on first-principles theory. The choice of the Kohn–Sham potential is a critical issue. It is found that standard gradient corrected functionals often yield the correct shape of the spectrum, but the computed excitation energies are systematically underestimated for the samples being studied. The recently developed exchange-correlation potentials “GRAC” and “SAOP” often yield much better agreement here with experiments for the excitation energies. The rotatory strengths of individual transitions are usually improved by these potentials as well.