Response properties from frozen-density embedding approximate second-order coupled-cluster theory

Abstract

We present an implementation of the coupled frozen-density embedding (FDEc) formalism for the calculation of ground-state and excited-state properties, linear-response properties, and transition moments with the coupled cluster with the singles and approximate doubles (CC2) model. Following the general strategy introduced by Höfener and Visscher [J. Chem. Theory Comput.12, 549–557 (2016)], we derive the working equations needed for the evaluation of these properties and describe their implementation into our open-source quantum chemistry program, Serenity. Our implementation comprises both projection-based embedding as well as embedding based on non-additive kinetic-energy functionals and the corresponding potentials. It makes use of the resolution-of-the-identity technique and features—in addition to CC2—the algebraic diagrammatic construction scheme of second order, ADC(2), as well as spin-component-scaled and scaled-opposite spin versions of CC2 and ADC(2). We demonstrate the capabilities of this FDEc framework by analyzing excitation energies, singlet and triplet excitation-energy splittings as well as oscillator strengths of excitonically coupled dimers, the excited-state/difference dipole moment of a formaldehyde⋯water system, and the optical rotatory dispersion of a microsolvated organic chromophore. In the latter case, we reconsider the case of (P)-dimethylallene· (H2O)2, for which uncoupled CC2-based frozen-density embedding fails, while FDEc-time-dependent density-functional theory showed promising results in earlier work. Here, we can confirm that the inclusion of system–environment response couplings leads to agreement with supermolecular CC2 results, highlighting the importance of inter-subsystem couplings in response-property calculations for molecular aggregates.