Raman optical activity spectra of chiral transition metal complexes

Abstract

We present calculated vibrational Raman optical activity (ROA) spectra for the transition metal complexes Λ-tris(acetylacetonato)cobalt(III), Λ-tris(acetylacetonato)rhodium(III), dichloro-(6 R,7 S,9 S,11 S-(−)-sparteine)zinc(II) and Δ( δδδ)-tris(ethylenediaminato)cobalt(III). For this study, it was necessary to benefit from density-fitting techniques to a large extent. Necessary implementations are described and the gauge origin problem is addressed. The importance of the electric-dipole–electric-quadrupole polarizability tensor for ROA intensity differences is investigated and found to be small, especially at lower wavenumbers where no C–H stretching vibrations occur. Furthermore, the basis set and density functional dependence is examined.