The use of Coulomb-attenuated methods for the calculation of electronic circular dichroism spectra

Abstract

We explore different parametrizations of the Coulomb-attenuated method B3LYP functional (CAM-B3LYP) for the calculation of circular dichroism spectra. In order to assess the performance of the different parametrizations, the calculated results are compared with high-level coupled-cluster calculations at the CC2 and CCSD levels of theory. We demonstrate that it is not possible to directly obtain good results both for the excitation energies and the rotational strengths simultaneously for any of the parametrizations of the CAM-B3LYP functional that we have tested. However, using the lowest excited state as a reference instead of the ground state—that is, shifting uniformly all excitation energies—leads to one parametrization which performs better than the others and thus can be recommended for studies of circular dichroism using the CAM-B3LYP functional.