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Coupled-cluster response theory offers a path to high-accuracy calculations of spectroscopic properties, such as magnetic circular dichroism (MCD). However, divergence or slow convergence issues or are often encountered for electronic transitions in high-energy regions with a high density of states. This is here addressed for MCD by an implementation of damped quadratic response theory for resolution-of-identity coupled cluster singles-and-approximate-doubles (RI-CC2), along with an implementation of the MCD A term from resonant response theory. Combined, damped and resonant response theory provide an efficient strategy to calculate MCD spectra over a broad frequency range and for systems that include highly symmetric molecules with degenerate excited states. The protocol is illustrated by application to Zink Tetrabenzoporphyrin in the energy region 2–8 eV and comparison to experimental data. Timings are reported for the resonant and damped approaches, showing that the greater part of the calculation time is consumed by the construction of the building 1blocks for the final MCD ellipticity. A recommendation on how to utilize the procedure is outlined.

We present a computational study of static and dynamic linear polarizabilities in solution. We use different theoretical approaches to describe solvent effects, ranging from quantum mechanics/molecular mechanics (QM/MM) to quantum embedding approaches. In particular, we consider non-polarizable and polarizable QM/MM methods, the latter based on the fluctuating charge (FQ) force field. In addition, we use a quantum embedding method defined in the context of multilevel Hartree-Fock (MLHF), where the system is divided into active and inactive regions, and combine it with a third layer described by means of the FQ model. The multiscale approaches are then used as reference wave functions for equation-of-motion coupled cluster (EOM-CC) response properties, allowing for the account of electron correlation. The developed models are applied to the calculation of linear response properties of two organic moieties -- namely, para-nitroaniline and benzonitrile -- in non-aqueous solvents -- 1,4-dioxane, acetonitrile, and tetrahydrofuran. The computed polarizabilities are then discussed in terms of the physico-chemical solute-solvent interactions described by each method (electrostatic, polarization and Pauli repulsion), and finally compared with the available experimental references., 13 pages, 9 figures