Theoretical study of the Raman optical activity spectra of [M(en)₃]3+ with M = Co, Rh

Vibrational Raman optical activity (ROA) spectra were calculated under off-resonance, near-resonance, and at-resonance conditions for (Formula presented.) (A) and under off-resonance conditions for (Formula presented.) (B) using a new driver software for calculating the ROA intensities from complex (damped) time-dependent linear response Kohn-Sham theory. The off-resonance spectra of A and B show many similarities. At an incident laser wavelength of 532 nm, used in commercial ROA spectrometers, the spectrum of A is enhanced by near-resonance with the ligand-field transitions of the complex. The near-resonance spectrum exhibits many qualitative differences compared with the off-resonance case, but it remains bi-signate. Even under full resonance with the ligand-field electronic transitions, the ROA spectrum of A remains bi-signate when the electronic transitions are broadened such as to yield absorption line widths that are comparable with those in the experimental UV-vis absorption and electronic circular dichroism spectra.