Modern electronic structure approaches facilitate unprecedented predictions on complex chemical systems. These capabilities call for tools to analyze the molecular mechanisms giving rise to the predicted properties in a well-defined, transferable fashion. We present a general quantum chemical approach to decompose any given molecular linear response property into individual contributions corresponding to fundamental intermolecular interactions such as electrostatics, polarization/induction, and charge transfer. To this end, we have developed a non-orthogonal formulation of linear response theory to allow (de)selecting individual contributions from intermolecular interactions or from individual subsystems, while retaining all remaining interactions. This approach helps develop a molecular understanding of molecular response properties, distinguish pair-wise and cooperative effects, and identify quantitative structure-property relations. Most importantly, our approach is based on fundamental (inter)molecular interactions that provide transferable descriptors for different chemical environments, such as solvents or molecular crystals. Our implementation within the <i>libresponse</i> open-source library is agnostic toward the choice of basis and interfaces with any quantum chemistry package using a local(izable) basis representation. We present illustrative results for molecular polarizabilities and spectroscopic signatures. Furthermore, we demonstrate the usefulness of decomposition approaches to develop quantitative structure-spectra relations for vibrational signatures of carbon dioxide solvated in ionic liquids and to provide design rationales for ionic liquids for use in carbon capture and CO<sub>2 </sub>electroreduction.

First-principles derived descriptors for linear response properties

254th National Meeting (2017)

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