Calculating Molecular Polarizabilities Using Exact Frozen Density Embedding with External Orthogonality.

Frozen density embedding (FDE) with freeze-thaw cycles is a formally exact embedding scheme. In practice, this method is limited to systems with small density overlaps when approximate nonadditive kinetic energy functionals are used. It has been shown that the use of approximate nonadditive kinetic energy functionals can be avoided when external orthogonality (EO) is enforced, and FDE can then generate exact results even for strongly overlapping subsystems. In this work, we present an implementation of exact FDEc-EO (coupled FDE TDDFT with EO) for the calculation of polarizabilities in the Amsterdam density functional program package. EO is enforced using the level-shift projection operator method, which ensures that orbitals between fragments are orthogonal. For pure functionals, we show that only the symmetric EO contributions to the induced density matrix are needed. This leads to a simplified implementation for the calculation of polarizability that can exactly reproduce the supermolecular TDDFT results. We further discuss the limitation of exact FDEc-EO in interpreting subsystem polarizabilities due to the nonunique partitioning of the total density. We show that this limitation is due to the fact that subsystem polarizability partitioning is dependent on how the subsystems are initially polarized. As supermolecular virtual orbitals are exactly reproduced, this dependence is attributed to the description of the occupied orbitals. In contrast, for excitations of subsystems that are localized within one subsystem, we show that the excitation energies are stable with respect to the order of polarization. This observation shows that impacts from the nonunique nature of exact FDE on subsystem properties can be minimized by better fragmentation of the supermolecular systems if the property is localized. For global properties like polarizability, this is not the case, and nonuniqueness remains independent of the fragmentation used.