Analytical Nuclear Excited-State Gradients for the Second-Order Approximate Coupled-Cluster Singles and Doubles (CC2) Method Employing Uncoupled Frozen-Density Embedding.

Abstract

We report the derivation and implementation of analytical orbital-relaxed properties and nuclear gradients for excited states using the second-order approximate coupled-cluster singles and doubles (CC2) model combined with uncoupled frozen-density embedding (FDEu). An implementation of the algebraic diagrammatic construction through second-order ADC(2), which arises from simplification of RICC2 FDEu, is also presented. In order to ensure a RICC2 FDEu Lagrange functional that is linear in the Lagrange multipliers, the Hartree-Fock density is employed for the target subsystem in the embedding contributions. The accuracy of the new scheme is assessed using the carbon monoxide molecule, 4-aminophthalimide, and a benzonitrile dimer, revealing that the obtained errors are below the method error of RICC2. Using density functional theory for the environment, the efficiency of the new method is illustrated by computing the perturbed excited-state dipole moment of a chromophore in a biological environment. For this system, comprising 32 molecules consisting of 366 atoms in total, the computation requires only a couple of days on a standard compute node. RICC2 FDEu thus enables large-scale calculations of ab initio wave functions for molecules in complex environments as routine applications.