Including vibrational effects in magnetic circular dichroism spectrum calculations in the framework of excited state dynamics.

Abstract

In this work, we present a computational approach that is able to incorporate vibrational effects in the computations of magnetic circular dichroism (MCD) spectra. The method combines our previous implementations to model absorption as well as fluorescence and phosphorescence spectra in the framework of excited state dynamics with a new technique to calculate MCD intensities, where molecular orientational averages are treated via semi-numerical quadrature. The implementation relies on a path integral approach that is employed to compute nuclear dynamics under the harmonic oscillator approximation (accounting for the nuclear potential energy surface) together with quasi-degenerate perturbative theory (to include the perturbation of an external magnetic field). We evaluate our implementation with a selected molecular set consisting of five aromatic organic molecules, namely, 1,4-benzoquinone, naphthalene, 2-naphthylamine, 2-naphthaldehyde, and benzene; we also included the MnO4- and the [Co(NH3)6]3+ transition metal complexes. This set is used to validate the ability of the approach to compute MCD A- and B-terms in conjunction with time-dependent density functional theory. The computed intensities are discussed in terms of the overall quality of the electronic structure treatments, vibrational modes, and the quality of the nuclear Hessians. It is shown that in the cases in which the potential energy surface is accurately represented, electric dipole-forbidden transitions are vibrationally activated, producing intensities relative to the dipole-allowed transitions in the same order of magnitude as the experimental measurements.