Approximate versus Exact Embedding for Chiroptical Properties: Reconsidering Failures in Potential and Response

摘要

We investigate the suitability of subsystem time-dependent density-functional theory (sTDDFT) for describing chiroptical properties with a focus on optical rotation parameters. Our starting point is a new implementation of the recently proposed projection-based, coupled frozen-density embedding (FDEc) framework. We adapt the generalized, non-Hermitian formulation of TDDFT and derive corresponding expressions for regular and damped response properties from subsystem TDDFT. We verify that our implementation of this "exact" formulation allows to reproduce supermolecular results of electronic circular dichroism (ECD) spectra, of optical rotatory dispersion, and of polarizabilities. We present a systematic test of the main approximations typically introduced in practical frozen-density embedding (FDE) calculations of response properties: (i) the use of approximate nonadditive kinetic-energy (NAKE) functionals, which can be avoided through projection techniques, (ii) the use of monomer (subsystem) basis sets rather than supersystem basis sets, and (iii) the neglect of intersubsystem response coupling within the so-called uncoupled FDE (or FDEu) approximation. While approximation (i) is known to generally lead to large errors for covalently bound subsystems, we present cases in which either the basis set or the coupling step are similarly or even (much) more important. In particular, we explicitly demonstrate by comparison to a fully coupled calculation that missing intersubsystem response couplings are responsible for the failure of FDE reported in a previous study [J. Chem. Theory Comput. 2015, 11, 5305-5315]. We show that good agreement with reference results can be obtained in this case even with standard NAKE approximations for the FDE potentials and efficient monomer basis sets, making calculations for larger systems well accessible.