On the rank-reduced relativistic coupled cluster method

Abstract

The efficiency of the Tucker decomposition of amplitude tensors within the single-reference relativistic coupled cluster method with single and double excitations was studied in a series of benchmark calculations for (AuCl)n chains, Aun clusters, and the cluster model of solid YbCl2. The 1 kJ/mol level of accuracy for correlation energy estimates of moderate-size systems and typical reaction energies can be achieved with relatively high compression rates of amplitude tensors via rejecting singular values smaller than ∼10−4. For the most extensive system studied (the YbCl7 cluster used for modeling of the ytterbium center in the ytterbium dichloride crystal), only ∼3% of compressed double amplitudes were shown to be significant. Thus, the rank reduction for the relativistic coupled cluster method with single and double theory, improving its computational scaling, is feasible. The advantage (if not necessity) of using the Goldstone diagrammatic technique rather than the “antisymmetrized” Brandow one is underlined. The proposed approach is promising for high-precision modeling of relatively large systems with heavy atoms.