The high-degree polynomial scaling of the most reliable quantum chemical models such as coupled cluster theory can be at least partly ameliorated via localized-orbital methods such as the projected-atomic-orbital (PAO) approach, local pair-natural-orbitals (LPNOs), orbital-specific virtuals (OSVs), fragment-molecular orbital (FMO) methods, the incremental scheme, etc. These methods typically yield thermochemical properties with an accuracy comparable to their canonical-orbital counterparts. However, their fidelity for higher-order properties � e.g., those depending on the derivative of the wave function with respect to external electric and magnetic fields � has been explored relatively little. In this talk, we will present our most recent findings in this area, particularly for chiroptical properties such as optical rotations and circular dichroism spectra, the accurate prediction of which is vital for the assignment of absolute sterochemical configurations.

On the non-locality of higher-order molecular properties: Challenges for reduced-scaling models

248th National Meeting (2014)

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